abstract book - raci centenary · pdf filestrength and thermal conductivity ......

Abstract Book

1

Floating Catalyst Chemical Vapor Infiltration of Nanofilamentous Carbon Reinfoced Carbon/Carbon Composites: Integrative Improvement on The Mechanical and

Thermal Properties

Cui Hong, Zhang Xiaohu, Deng Hailiang

Presenting author’s e-mail: [email protected]

Xi’an Aerospace Composites Research Institute, Xi’an, PR China Nanofilamentous carbon (NFC) reinforced carbon/carbon composites were produced by floating catalyst film boiling chemical vapor infiltration from xylene pyrolysis with increasing ferrocene content from 0 to 2.0 wt%. The effects of the catalyst content and heat treatment on the mechanical and thermal properties were investigated. Results show that the grown NFCs and increased degree of graphitization derived from the present floating catalyst make an integrative improvement on the mechanical and thermal properties. The composites produced at 0.5-0.8 wt% catalyst content have unique combination of higher strength and thermal conductivity (TC), and lower coefficient of thermal expansion (CTE). The reinforced rough laminar (RL) pyrocarbon (PyC) matrix and bridged pores by NFCs, coupled with the pull-out of NFCs, conduce to an evident toughness increase. When the catalyst content exceeds 0.8 wt%, the strength and TC are decreased by the limited NFC growth and the matrix transformed from RL to isotropic PyC. The Fe3C phase and limited NFC growth induce a CTE increase at the higher catalyst contents. After the treatment at 2500 ºC, the strength and CTE reduce, while the toughness and TC are remarkably enhanced. The flexural and interlaminar shear strength retention ratios achieve a superior value about 73.1-74.5 % and 79.1-79.4 % at 0.5-0.8 wt% catalyst contents, respectively; the maximum TC in the out-of-plane and in-plane is 72.5 and 339.1 W/(m·K). Relatively low CTE is obtained at 2.0 wt% catalyst content, which results from the increased thermal cracks and pores.

2

Nanoscale Environment-Interactive Carbon Engineering

Kaneko, K

e-mail: [email protected] Shinshu University, Nagano, Japan

Graphene of surface area of 2630 m2g-1 offers -conjugated bi-surfaces, providing the strongest dispersion interaction per unit weight. Therefore, the graphene-based carbon materials have been widely applied to various surface sensitive technologies. We need to get an essential understanding and tuning of the interfacial properties of graphene based carbons. This presentation will introduce recent following studies. Highly efficient separation of 18O2 and 16O2 isotopic molecules: 18O is indispensable to the positron emission tomography for cancer therapy. The classical separation selectivity is the order of 1.003. Low temperature adsorption method of oxygen isotopes using nanoporous carbons gives more than 200 times higher selectivity than the classical separation. Non-Coulomibic Ion Structure: Supercapacitors technology has requested structural understanding of ions confined in carbon nanopores. We transformed 1D synchrotron X-ray scattering information to the plausible 3D structure information through hybrid reverse Monte Carlo simulation, getting the component structure on cations and anions. This study evidenced the non-Coulombic accumulation of ions having the same charge in 0.7 nm-pores, supporting the super-ionic state theory. Smart nanowindows: Nitrogen molecules at 77 K can more rapidly penetrate the nanowindows of 0.4 nm than argon at 87 K. Nitrogen molecules are trapped by the quadrupole-local electric filed interaction enough long to accept further nitrogen molecules (quasi-wall effect). Also a new concerted nanowindow rim motion-aided separation mechanism is proposed. SWCNT dispersant: Newly developed Zn/Al sol-gel dispersant can disperse the SWCNT bundles to produce a highly stable SWCNT ink, which leads to transparent conducting film and stretchable electrodes.

3

A New Family of Transition Metal/N-Doped Carbon for Efficient CO2 Electroreduction

Hao, G-P1,2, Ju, W3, Bagger, A4, Rossmeisl, J4, Strasser, P3, Kaskel, S1


1 Department of Inorganic Chemistry, Technische Universität Dresden, Bergstraße 66, Dresden 01062, Germany

2 National Graphene Institute, University of Manchester, Oxford Road, Manchester, M13 9PL, UK

3 Department of Chemistry, Chemical Engineering Division, Technical University Berlin, Straße des 17. Juni 124, 10623 Berlin, Germany

4 Department of Chemistry, University of Copenhagen, Universitetsparken 5, Copenhagen, Denmark

Direct electrochemical reduction of CO2 has emerged as a potential way to convert CO2 into useful chemical and fuels. This process is particularly interesting since it allows to use the surplus of renewable electricity to react water and waste CO2 to produce CO and hydrocarbons. Here, we present new and important advances in our rational understanding of the selective electrocatalytic CO2-to-CO reduction process on N-coordinated, non-noble metal- doped porous carbons (M-N-C, M=Mn, Fe, Co, Ni, Cu). These materials are single-site catalysts comprising active porphyrin-inspired M-Nx moieties. We investigate the trends in their intrinsic electrochemical reactivity, CO turnover frequencies, and CO efficiencies and demonstrate that Fe-N-C and especially Ni-N-C catalysts outperform today’s state-of-art Au and Ag catalysts. We then model the catalytic active site of the carbon materials using Density Functional Theory (DFT), contrast their theoretical and experimental reactivity-selectivity descriptors, and arrive at a fully consistent atomic-scale understanding of their potential-dependent CO and hydrocarbon selectivity. Linking DFT predictions directly with experiments we provide a mechanistic explanation why Fe-N-C and Ni-N-C represent highly cost-effective, energy-efficient, and earth-abundant carbon-based catalysts for generation of pure CO streams inside CCCs. In broader terms, our framework also provides useful predictive guidelines for the rational design of selective carbon-based CO2 reduction catalysts.

4

A New Route to Produce Free Standing Graphene-Based Films

Pérez-Mas, AM1, Sánchez-Hidalgo, R1, Zambrano-Andazol, I2, González, Z1, Meana, A2,3, Menéndez R1

[email protected]

1Instituto Nacional del Carbón, INCAR-CSIC, Oviedo, Spain 2Instituto Universitario Fundación Fernández -Vega, Oviedo, Spain.

3Universidad de Oviedo, Oviedo, Spain.

Nowadays there are different methods for preparing free standing graphene-based films most of them starting from graphene oxide (GO). Most of these films are known to have extraordinary mechanical properties. It has been reported that their stability in water is due to the presence of some useful contaminants, derived from the filters used for film formation, e.g. the presence of aluminium in the anodic aluminium oxide (AAO) membrane filters. One of the promising applications of graphene-based membranes is as substrates for cell growing. Therefore, pure graphene-based films with high wettability and stability in aqueous media are required. This study investigates the development of novel free standing GO films with suitable properties for cell growing. Films were obtained by vacuum filtration of a GO water suspension followed by different reduction procedures such as chemical reduction with hydriodic acid or ascorbic acid, thermal reduction at different temperatures or electrochemical reduction. The resulting films were characterized by FTIR, XRD, XPS and SEM. Additionally, the tensile strength of the films was also evaluated. The results show that the GO films initially obtained (non-reduced), with no presence of contaminants, exhibit high Young’s Modulus (12±2GPa) and good wettability due to their high oxygen content (50 wt %). Nonetheless, despite the wettability and tensile strength decrease after the chemical and thermal reduction processes, the resultant films were still found to be suitable for promoting cell growing.

5

A Novel Photoreduction of Copper Acetate Confined in Carbon Nanospace

Ohkubo, T1, Okamura, W1, Yumura, T2, Kuroda, Y1


1 Okayama University, Okayama, Japan 2 Kyoto Institute of Technology, Kyoto, Japan

We have succeeded in revealing specific coordination structure of nano-restricted metal acetates in carbon nanospaces. For instance, interatomic distance between metal atoms of a copper acetate monohydrate molecule, which is a dinuclear metal complex forming Cu2(OAc)4·2H2O, is elongated in the nanospace of activated carbons. Interestingly, we can induce visible-light photoreduction of copper acetate which is confined with water in the nanospace; Cu2O nanoparticles can be synthesized. Since metal-to-ligand charge-transfer (MLCT) is typically initiated under UV-light region, the reduction under visible-light irradiation must be therefore launched with distinct processes. Herein, we discuss a possible mechanism of the synthetic route from hydrated copper acetate to Cu2O in the nanospace of single-walled carbon nanotube (SWCNT). In the present study, we have used highly purified SWCNT whose diameter is around 2.0 nm. Absorption bands around 8981 eV, which cannot be observed in the spectra of any crystal forms or aqueous solution of copper acetate, could be specifically observed in the XANES spectrum of copper acetate co-adsorbed with water into the nanospace of SWCNT under a dark condition. The result of the appropriate DFT calculation demonstrated the elongation of the Cu-Cu distance of Cu2(OAc)4·2H2O which coincides with the structure obtained by the EXAFS analysis. Furthermore, TD-DFT result also gave a novel absorption band around 420 nm assigned to the LMCT of Cu2(OAc)4·2H2O in the model nanospace. Thus, the present results strongly indicate that specific formation of hydrated copper acetate formed in the nanospace is a key step to synthesize Cu2O nanoparticles under the visible-light irradiation.

6

A Novel Template-Free Design for Monodisperse Yolk-Shell Structured Metal@Carbon Nanospheres

Xu, F 1, 2, Lu, Y1, Ma, J1, Fu, R1, and Wu, D*1


1 Sun Yat-sen University, Guangzhou, China a 2 Northwestern Polytechnical University, Xi’an, Chin

Yolk-shell nanostructures, representing multiple-discrete functional components incorporated in one unit, have been one of the most fertile arenas in materials chemistry. However, the commonly used multi-step synthetic templating approach involving selective etching of interlayers is essentially tedious and harsh. Thus it remains a challenge to develop versatile strategies without sacrificial templates. Here we report a general template-free prototype to construct novel yolk-shell structures, which is based on the confined interfacial copolymerization of aniline and pyrrole at TritonX-100 interface in the presence of core nanospheres. Our proposed strategy greatly simplifies synthetic routes, yields uniform nanospheres with controllable diameters, and achieves highly porous carbon shells. Benefiting the structural features, the novel yolk-shell Au@HCNs showed potential applications as efficient heterogeneous catalysts in the reduction of 4-nitrophenol and nitrobenzene. We believe our finding presented here may open up a new route with great extendibility for producing yolk-shell nanostructures with various functional cores, which could find widespread applications.

7

A rechargeable high-energy Li-ion Al/S battery incorporating sulfurized polyacrylonitrile and alloy

Sun, J1, Zeng, Q-C1, Amal, R1, Wang, D-W1*


1 University of New South Wales, Sydney, Australia

Polysulfides shuttle (PS) phenomenon is always a dominate problem which blocks commercial application of Li-S battery. Carbon materials have been serving sulfur in cathode for decades with their diverse porosity together with the conductivity originated from graphitic structure. In this study, sulfur was introduced into a polyacrylonitrile-derived carbon backbone by vulcanizating under the protection of inner gas. The sulfurized-polyacrylonitrile (SPAN) contains short sulfur chains covalently binding to the carbon surface, demonstrating extraordinary stability and rate capability. From another aspect, aluminium (Al) is an appealing anode material for the sake of its high capacity, natural abundance, and safety. Pairing Al with sulfur (S) has been regarded as a promising strategy to achieve high-energy rechargeable batteries. Therefore, a Li-ion Al/S battery is constructed by using a sulfurized polyacrylonitrile cathode, commercial carbonate electrolyte, and an Al-Li alloy anode, which allows a relative high working voltage (1.5V). The reaction mechanism is verified by using electrochemical and spectroscopic analyses which show that the charge carriers shuttling between two electrodes are the lithium ions. The specific energy of the full cell based on the total weight of active materials is estimated to be 589~762 Wh/kg depending on the alloy composition. The Li-ion Al/S battery exhibits good reversibility and stability, with a slow decaying rate at 0.09% per cycle.

8

A Reversible Crosslinking Structure in Polyacrylonitrile Fibers Duing Heating in Inert Atmosphere

Fei Huang, Liangxiao Zhou, Weizhe Zhao, Yonggen Lu


Donghua University, Shanghai, China

It is found that chemical crosslinking take place between nitrile groups of adjacent polyacrylonitrile molecules by heating at temperature between 170-230 in inert atmosphere, which is proved by its insolubility in concentrated sulfuric acid. However, after heat treatment in an inert atmosphere above 230 for one hour, the derived fibers become resolvable again in sulfuric acid, meaning the formed crosslinking structure, probably -C=N-N=C- bonds, is reversible. Oxygen in the atmosphere inhibit such a kind of crosslinking even oxidation is necessary for a thermostable and irreversible structure.

9

Activated carbons with simultaneously high surface area and pore volume

Luis Estevez1, Adam L Garcia1, Venkateshkumar Prabhakaran1, Wu Xu1, Priyanka Bhattacharya1, Yongsoon Shin1, Ji-Guang Zhang1

[email protected]

1 Pacific Northwest National Laboratory, Richland, WA USA

Herein, we present a strategy for the synthesis of a porous carbon material with a simultaneously very high surface area (>2500 m2/g) and colossally large pore volume (~10 cm3/g). We will show how we achieved these uniquely combined textural characteristics by utilizing a hierarchically porous carbon (HPC) material with both macropores and mesopores via ice templating and a hard silica template, respectively; and then by further tuning the morphological structure via physical (CO2) activation of the HPC. Furthermore, we will demonstrate how we are able to replicate these distinctively high textural properties in both a disordered/hard carbon based HPC, as well as a more ordered/graphitic HPC.

10

Activated Graphene-like Carbons Derived from Biomass for Electrochemical Capacitors

Kim, T1, Jung, S. H.1, Park, S. J., Lee, H. S.1, Kim, B. N.2, Yoo, I. K.2


1 Gachon University, Seongnam 13120, South Korea 2 Electronics and Telecommunications Research Institute, Daejeon 34129, South Korea

We report a scalable and cost-effective method to produce highly porous and three-dimensionally structured graphene-like carbons derived from biomass precursors. Among diverse carbon sources, carbohydrate derivatives (e.g. glucose, sucrose, and cellulose) were selected as a low-cost carbon precursors. These precursors were heated up with ‘gas releasing’ salts, during which the precursors were polymerized and blown by released gas into bubbles. The polymer bubbles were then heated up to a high temperature and converted into a three-dimensional (3D) carbons composed of graphene-like thin walls. We further attempted to activate these carbons to introduce a large number of nanoscale pores, thereby achieving high surface area. These carbons were then utilized as electrode for electrical double layer capacitors (EDLCs). The highly porous activated graphene-like carbons from biomass precursors showed a high gravimetric specific capacitance of up to ~150 F/g in an organic and ionic liquid electrolyte. The electrochemical performances of the electrode materials will also be presented in terms of energy density, power density, and cycle life.

11

Activation-free and no more post-treatment to biomass-based highly porous carbon

Liang, Y, Li, W, Liu, Y


College of Materials and Energy, South China Agricultural University, Guangzhou 510642, P. R. China

Highly porous carbon materials are of great interest for a wide range of important applications. Many examples for their synthesis exist, but these synthetic processes can be quite complex and also very time consuming. There is still a major challenge to develop a facile yet versatile conceptual approach to produce them. Here, we present an efficient, activation-free, post-treatment-free strategy for the synthesis of highly porous carbon by a simple carbonization of a mixture of biomass and polytetrafluoroethylene (PTFE) powder. PTFE employed here can in-situ generate HF to etch out natural silica during carbonization treatment of biomass like rice husk and reed leave. This strategy not only reduces synthesis procedure by combining post-silica-removal and carbonization in a single step, but also completely eliminates the usage of hazardous HF or corrosive NaOH. The as-synthesized carbon materials possess a BET surface area as high as 2051 m2/g without any activation treatment, which is about 20 times enhancement in porosity compared to the traditional biomass-based carbon materials. Owing to their well-developed porosity and valuable hierarchical porous morphology, highly porous carbon developed in this study hold great promise in a spectrum of applications. These findings could provide a new avenue for the facile and efficient production of high-performance porous carbon materials with promising applications in various fields.

12

Adsorption and desorption of ssDNA from single walled carbon nanotubes

Shearer, C, Yu, L, Fenati, R, Ellis, A, Andersson, G, Shapter, J


Flinders University, Adelaide, Australia

Here we first discuss the use of specific ssDNA oligonucleotides for the purification of single walled carbon nanotubes (SWCNTs) by chirality using aqueous two phase separation. SWCNTs with (n, m) of (8, 4), (6, 5), (7, 5) were purified and characterised using AFM, Raman, photoluminescence and UV-Vis spectroscopy. Post-processing of the SWCNT-ssDNA hybrids was completed to determine an effective method to remove the ssDNA after separation. We compare biological, physical and chemical methods for subsequent desorption of ssDNA on the basis of facility and simplicity. It was found that an enzyme (Exonuclease 1) could effectively remove the phosphate backbone from ssDNA as confirmed by photoemission spectroscopy and zeta potential but could not completely remove ssDNA nucleotides. Physical heating of the sample up to 500 oC was not able to desorb the strongly adhered ssDNA. Various chemical treatments such as exposure to high or low pH and oxidising environments were found to effectively desorb the ssDNA from the SWCNTs, leaving them pristine as confirmed by fluorescence microscopy and photoemission spectroscopy. These findings will allow the effective removal of ssDNA from SWCNTs for application in a range of electronic and optic devices.

13

Adsorption behavior of mixtures of organic vapors on activated carbon.

Boutillara, Y1,2, Berezovska, I1,3, Lodewyckx, P1, Van Riet, R1


1 Department of Chemistry, Royal Military Academy, Renaissancelaan 30, 1000 Brussels, Belgium

2 Thermodynamics department, Faculty of Engineering, University of Mons, 20 Place du Parc, 7000 Mons, Belgium

3 Macromolecular Materials Laboratory, Department of Materials Science and Engineering Technion – Israel Institute of Technology

Haifa 32000, Israel

Activated carbon filters are designed to retain various types of gases and vapors such as organics in single form and/or in mixtures. Understanding the adsorption of mixtures of organic compounds is very important by the fact that it is quite common for the carbons to be solicited by a mixture of vapors rather than a single one. In this context, the present work deals with activated carbon filters exposed to different binary mixtures of organic vapors under varying conditions of concentration and flow rate as close as possible to their real use. It is assumed that the adsorption behavior of binary mixtures inside activated carbon filters is regulated by competition phenomena. The visual result of the latter is the roll-up effect in the breakthrough curves. The aim is to evaluate from the breakthrough curves the effect of different parameters on the behavior of each vapor in a mixture and on the breakthrough time. Subsequently, an eventual theoretical estimation of the capacity of adsorption for the vapors in a mixture is intended. To attain these goals, two different activated carbons are selected in order to obtain a better generalization of the results observed.

14

Advantages of NEXAFS over XPS and FTIR for carbon surface characterization.

Kenneth G. Latham1, Michela I. Simone, Wesley M. Dose2, Jessica A. Allen1, Scott W. Donne1


1 University of Newcastle, Newcastle, Australia 2Argonne National Laboratory, Argonne, Illinois, USA

The quantitative and qualitative determination of surface functionalities is vital to understanding how carbon surfaces interact in several applications (i.e., catalysis, electrochemistry). To achieve this, Fourier Transform Infra-Red (FTIR) and X-ray Photoelectron Spectroscopy (XPS) are commonly used to understand the functionality present on the surface of carbon structures. However, both techniques can suffer considerably in resolution and produce broad peak shapes when applied to amorphous carbons or carbon surfaces with a wide range of functionalities. Synchrotron based Near Edge X-ray Adsorption Fine Structure (NEXAFS) can overcome the analysis obstacles present in FTIR and XPS. The advantage of NEXAFS in examining low-atomic number elements (e.g., carbon and nitrogen) is that the energy differences between the resonant X-ray excitations of core-level (1s) electrons to unoccupied orbitals or continuum levels (either π* or σ*) are readily resolvable. Additionally, these excitations that are observed in K-edge spectra of low-atomic number elements are directly related to the chemical environment of the absorber, including its oxidation state. Overall, this results in the presence of resolvable, structure-dependent resonances in these spectra that can provide additional information about the chemical structure of amorphous carbons not present in XPS and FTIR. To examine the benefits of this technique, carbon, oxygen and nitrogen XPS and NEXAFS spectra from hydrothermally carbonized and activated carbons is compared. Additionally, different methods for the analysis of NEXAFS spectra are also examined.

15

Synthesis and characterization of aluminum carbide-derived carbon with residual aluminum-based nanoparticles

Moran, C1, Marti, R2, Hayes, S2, Walton, K1


1Georgia Institute of Technology, Atlanta, United States 2Washington University, St. Louis, United States

An in-depth study on the etching process for producing carbide-derived carbons from aluminum carbide (Al4C3) has been performed. These materials were investigated at a range of etching temperatures and times, examining carbon and residual aluminum content for their respective properties. By altering the etching time and temperature, the surface area, residual aluminum content, and pore size distribution can be tuned. A maximum surface area of 1126 m2 g−1 was observed for materials etched at 500 °C for 1 h. The pore size has shown to be tunable from ≤0.7 to 8 nm. Interestingly, aluminum-based nanoparticles were observed via TEM and SEM for partially etched samples, with evidence of tunable metal species on the surface of the Al4C3-CDC samples at different etching temperatures between 300 and 700 °C. Characterization of the aluminum species present over this temperature range took place using solid-state 27Al NMR for bulk analysis and XPS was implemented to investigate surface based particles. The formation of crystalline α-Al2O3 was observed at etching temperatures of 700 °C. The results of this work provide detailed synthesis strategies for controlling not only the porosity and surface area of a carbide-derived carbon, but also the extent and type of residual metal nanoparticles embedded in the final carbon matrix utilizing a one-pot synthesis.

16

Anarysis Of Three Dimentional Texture of Carbon Materials By Optical Microscopy and Image Processing

Oshida, K1, Fujinawa, T1, Tavanleuang, V1, Takahara, J2, Kimura, T2, Sasaki, R2,


1 National Institute of Technology, Nagano College, Nagano, Japan 2 Mitsubishi Chemical Group, Science and Technology Research Center, Inc., Yokohama,

Japan

The three dimensional (3D) texture of coal tar pitch-based cokes (pitch cokes) were revealed by optical microscopy (OM) and image processing of 3D construction. The pitch cokes are widely used in several industrial field. There is a significant correlation between the texture of pitch coke and its bulk properties. The pitch coke has very complex structure which consists of anisotropic, isotropic carbon domains and pores among them. These domains can be observed by OM as colorful images. In our previous study, we succeeded in quantifying complex pitch coke texture and estimating the physical properties of pitch cokes by applying color image processing. The pitch cokes were embedded in the transparent resin. The polished cross sections of them were observed by OM every 5μm or 10μm in the depth direction. Then images of 50 to 100 cross sections were obtained. The 3D images of the pitch cokes were constructed from stacking the sliced pitch coke images and the volume and the surface area of the anisotropic, isotropic carbon domains and pores were measured. 3D models of the pitch cokes were also manufactured by 3D printer. The 3D models indicate how the shapes of texture of carbon materials connected and disconnected. Thus the shapes of each domain were clarified. The results are expected to be useful to understand manufacturing situation and eventually, material design.

17

Anode Performance of Silicon Hybridized with Pitch-Derived Carbon

Fujimoto, H

[email protected]

Energy Technology Laboratories, Osaka Gas Co., Ltd.,

Since the first commercialization of Li ion battery, the combination of LiCoO2 cathode and graphite anode has been the major system, and the energy density has been enhanced up to more than twice as the initial value by the various improvements. The capacity of graphite anode attains almost the theoretical value of 372 Ah/kg. Hence, the further enhancement requires the material change from the graphite to the other materials with higher capacity. For such a reason, the Si/carbon composite anode has recently investigated. However, it has not been used for commercialization because of the limited cycling due to the particle size reduction during the charge/discharge reaction. In the present study, the Si was hybridized with pitch-derived carbon in order to improve the cycle degradation, and its anode performances were investigated. The obtained compound was the pure Si/C hybrid materials with no SiC phase. It exhibited fairly good cycle performance with about 700 – 800 Ahkg-1 even if the conventional binder system such as SBR/CMC was applied.

18

Antibacterial Activity of Graphene Oxide

H. Enis Karahan1, Yuan Chen2


1 Nanyang Technological University, Singapore 2 The University of Sydney, Sydney, Australia

Carbon-based nanomaterials have a great potential as novel antibacterial agents; however, their interactions with bacteria are not fully understood. This study demonstrates that the antibacterial activity of graphene oxide (GO) depends on the physiological state of cells for both Gram-negative and –positive bacteria. GO susceptibility of bacteria is the highest in the exponential growth phase, which are in growing physiology, and stationary-phase (non-growing) cells are quite resistant against GO. Importantly, the order of GO susceptibility of E. coli with respect to the growth phases (exponential >> decline > stationary) correlates well with the changes in the envelope ultrastructures of the cells. Our findings are not only fundamentally important but also particularly critical for practical antimicrobial applications of carbon-based nanomaterials. Reference: Nanoscale, 2016, 8, 17181

19

Anticancer Activity of Graphene on Cells from Myelomonocytic Leukemia Patients

Bianco Alberto

e-mail: [email protected]

University of Strasbourg, CNRS, Immunopathology and Therapeutic Chemistry, UPR3572, Strasbourg, France

Chemotherapy is still the most common treatment of cancer, one of the major causes of mortality in the world. However, serious frequent challenges are encountered by current cancer therapies including nonspecific systemic distribution, inadequate drug concentrations reaching the tumor, and severe side effects due to the high toxicity addressed unintentionally to healthy tissues. In this scenario nanotechnology could provide new tools for an effective treatment of cancer. One nanomaterial that is raising tremendous interest in the scientific community is graphene. Graphene is being explored for many potential medical applications due to its exceptional physicochemical characteristics. In this work we used a few-layer graphene (FLG) dispersion exfoliated from graphite by a mechano-chemical approach. We explored the biological impact of the FLG on multiple human immune primary cell populations. We found a specific impact on monocytes showing neither toxic nor activation effects on the other types of immune cells. Thanks to this intrinsic biological property, we further explored the possible therapeutic application of FLG on neoplastic monocytes, obtained from acute myeloid leukemia and chronic myelomonocytic leukemia patients. We demonstrated the unique ability of FLG to target and successfully boost the necrosis of monocytic cancer cells. Moreover, the comparison between FLG and the common chemotherapeutic drug, etoposide, confirmed the specificity and higher toxicity of graphene on cancer cells. These findings open the way to a possible application of FLG as a specifically targeted tool against neoplastic cells in myelomonocytic leukemia patients.

20

Antifouling Performance of Carbon Nanotube-Polyamide Nanocomposite Reverse Osmosis Membrane

Takizawa, Y1, Inukai, S1, Cruz-Silva, R1,2, Araki, T3, Akuzawa, N1, Takeuchi, K1,2, Endo,

M1,2


1 Global Aqua Innovation Center, Shinshu University, Nagano, Japan 2 Institute of Carbon Science and Technology, Shinshu University, Nagano, Japan

3 Research Organization for Information Science & Technology, Tokyo, Japan

Strong anti-fouling and self-cleaning properties against organic foulant were found in nanocomposite reverse osmosis membranes made of multi-walled carbon nanotube and polyamide (MWCNT-PA membrane). The bovine serum albumin (BSA) was labeled with fluorescein isothiocyanate (FITC) and used as model foulant, while a solution of NaCl was used to simulate a typical feed in a desalination process using a cross-flow system pressured at 0.7 MPa. Fouling process was studied by in-situ fluorescence microscope observation of the surface of membranes. BSA adsorption of the MWCNT-PA membrane was considerably lower than other commercial or laboratory made plain PA membranes. The degree of fouling assessed by fluorescent microscopy observations was in agreement with the permeation flux measurements. These tests showed that the permeate flux of plain PA membranes decreased by 30-50 % from the original value after the addition of BSA. However, the permeate flux of the MWCNT-PA membrane decreased by only 15 %, and it eventually recovered to the original value. Molecular dynamics simulation suggests that the addition of MWCNT to the PA enhanced the antifouling performance against BSA of the membrane by reducing the number of hydrogen bonds between the membrane surface and the BSA. The lower adhesion forces in presence of MWCNT results in a weaker interaction between the PA and the protein, and consequently, the adsorption of BSA. This work gives new insights into the antifouling mechanism of MWCNT-PA nanocomposite membranes.

21

Application of Magnetite Nanoparticles for Synthesis of Carbon Nanotubes by The CVD Method

Lesbayev A.1,3, Prikhodko, N1,2, Smagulova, G1,3, Lesbayev, B.T.1,3, Nazhipkyzy, M1,3,

Ustayeva G.S.1,Elouadi B.4, Mansurov, Z1,3


1 Institute of Combustion Problems, Almaty, Kazakhstan

2 Almaty University of Energetics and Communications, Almaty, Kazakhstan 3 Al-Farabi Kazakh National University, Almaty, Kazakhstan

4 Université de La Rochelle, La Rochelle, France Nanotechnology in recent years has become one of the most promising and fastest growing areas of science. The use of nanomaterials in medicine and pharmacology is a priority, which allows to solve the most urgent problems in these areas. Also, nanomaterials are used to improve certain characteristics of the materials. Such as shielding properties of electromagnetic radiation, to improve the mechanical properties and to obtain materials with specific optical properties. Currently, for the exploration and use of nanomaterials, there are many methods of their synthesis. Synthesis nanomagnetite chemical method is an easy, affordable and fast. The resulting particles range in size from 10 nm to 30 nm. spherical shape and have a small spread of sizes. Nanomagnetite can play the role of the first nanorobots to deliver drugs to specific locations of the body, using an external magnetic field exposure. Also, due to the magnetic properties can be added nanomagnetite in the structure of the polymer and a polymer-magnet, it will receive a very good insulating material of the electric current with magnetic properties. From this it can be assumed that the use of additives in the form of very acceptable. As well as their use as a catalyst for synthesizing carbon nanotubes CVD method. The synthesized carbon nanotubes can be used as additives to create a shielding material from electromagnetic radiation.

22

Australian Spinifex Nanocellulose Reinforced Polyacrylonitrile as Precursors for Carbon Fibers

Edward Jiang1, Minoo Naebe3, Darren J. Martin1


1Australian Institute for Bioengineering & Nanotechnology, The University of Queensland, St Lucia, Queensland, Australia

2Carbon Nexus, Deakin University, Institute for Frontier Materials, Geelong, Australia Ultra-lightweight and high strength carbon fiber composites have recently found considerably increasing demand for use in the automotive and aerospace sectors. However due to the high cost of the petroleum-derived polyacrylonitrile (PAN) precursor, as well as the energy input required for the carbonisation process, uptake of carbon fibers in adjacent sectors have been severely limited. The use of nanoparticles and nanofibers to reinforce the polyacrylonitrile precursor offers a new avenue for improving the efficiency of the carbonisation process to reduce costs. This work involves new high-performance carbon fibers prepared from PAN composite precursors reinforced with high aspect ratio cellulose nanofibers and cellulose nanocrystals, specifically derived from native Australian spinifex grass. To this end, various nanocellulose reinforcing agents on PAN-based carbon fibers was explored by wet spinning composite dispersions of PAN and nanocellulose, followed by stabilization carbonization of the fibers. Mechanical results indicate the potential for nanocellulose fillers to reinforce precursor PAN fibers, while initial Fourier-transform infrared spectroscopy and differential scanning calorimetry studies also highlight the effect of a cellulose-based filler in regulating the PAN cyclization reactions during the stabilization process. The effect of the aspect ratio of the nanocellulose on the carbon structure formation in these fibers will also be described. This work will provide the basis for future studies towards developing a more environmentally-friendly pure nanocellulose carbon fiber precursor.

23

Bending deformation of C70 nanowhiskers by liquid-liquid interfacial precipitation method

Hayase, H1, Yamamoto, S1, Saeki, T1, Murata, H1, Miyazawa, K2, Tachibana, M1

[email protected]

1 Yokohama City University, Yokohama, Japan 2 Tokyo University of Science, Tokyo, Japan

Nano/microcrystals of fullerenes such as C60 and C70 have attracted much interest due to their unique morphologies and properties. Various growth techniques such as liquid-liquid interfacial precipitation method (LLIP) have been developed to grow nano/microcrystals such as nanowhiskers (NWs) and nanosheet. However studies of C70 are much less than those of C60. In this study, we report the amount synthesis of longer C70 NWs by LLIP method and the unique mechanical properties. C70 NWs were prepared by the LLIP method with an interface between C70-saturated m-xylene and 2-propanol. As a result, we obtained very long C70 NWs exceeding 100 μm with 500 nm in diameter. X-ray diffraction and FT-IR showed that C70 NWs contain m-xylene and have orthorhombic structure. Additionally, it was clarified that the structure is transformed into face-centered cubic one after the evaporation of m-xylene by annealing at 140 ºC. On the other hand, the mechanical property exhibited large bending recovery where the radius of curvature for the bending was 5 μm. The characteristic feature is quite different from the brittleness of pure C70 bulk crystals. The mechanism of the unique elastic behaviour of C70 NWs will be discussed in light of their structure and solvation.

24

Bio-Inspired Polydopamine Chemistry for Effective Surface Modification of Carbonaceous Nanomaterials

Ye, G1, Song, Y1, Wang, J1


1 Collaborative Innovation Center of Advanced Nuclear Energy Technology, Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing, 100084, China

Surface engineering of carbonaceous nanomaterials provides vast opportunities to functionalize these intriguing materials for potential applications such as electrochemical capacitors, catalysis, adsorption, and drug delivery. In recent years, a large panel of techniques have been established to modify the surface properties of carbonaceous nanomaterials through generating chemical or biological functionalities on the surfaces. Among the various techniques, controlled growth of polymer brushes from the surface of nanomaterials by using atom transfer radical polymerization (ATRP) have been developed as an enabling tool for surface functionalization. This method is chemically versatile, compatible with both aqueous and organic media, and feasible for various functional monomers. But owing to the inert nature of carbonaceous nanomaterials, the attachment of the halogen-containing initiator molecules on the surfaces, which is the prerequisite for surface-initiated ATRP, remains a challenge. Typical methods for activating the inert surfaces involves the acid oxidation-acylating chlorination route or click chemistry, which is environmentally challenging and may cause damage to the structure of Substrate materials. Inspired by the adhesive behavior of mussel proteins, polydopamine (PDA) chemistry has been exploited as a versatile surface modification method, which provides an effective pathway for anchoring the initiator molecules on inert surfaces. We present here a new strategy for surface functionalization of carbonaceous nanomaterials by integrating the bio-inspired PDA chemistry and surface-initiated ATRP technique. The modified materials show enhanced hydrophilicity, good dispersibility, and binding ability toward uranyl ions, which may be of potential for environmental and other applications.

25

Biomass Carbons as Additives for Lubrication: Friction Reduction Key Parameters

Thomas, P1, Debaud, Y1, Nomede-Martyr, N1, Romana, L1

[email protected]

1 Groupe de Technologie des Surfaces et Interfaces (GTSI EA2432), Université des Antilles, Pointe-à-Pitre, France

In boundary lubrication regime, friction reduction and antiwear processes are associated to the presence of additives in the lubricating oils or greases. These processes are due to the formation of protective tribofilms resulting from chemical reactions between the additives and the sliding surfaces, in the physico-chemical conditions of the sliding contact. But the main problems encountered with conventional additives (transition metal dithiophosphates or carbamates) are their inefficiency in the case of non metallic surfaces and the film formation period (induction period), in which the contacting surfaces undergo sever wear. Recently developed lubrication strategies consist in the use of dispersion in oils of nano additives able to build the protective tribofilm in the sliding contact without reaction with the surfaces [1]. We pointed out in previous studies the good friction reduction properties of various (nano) carbon materials [2, 3]. This work is concerned with the use of activated carbons synthetized from biomass as new additives for lubricants. Special attention is paid to the role of the carbon structure, in terms of morphology, size, (nano)structuration, porosity of the carbon particles on the friction properties of the additives. 1 Mansot, J.L, et al, Brazil. J. of Phys. 2009, 39 2 Thomas, P, et al, Tribology Letters, 2011, 41 3 Thomas, P, et al, Tribology Letters, 2014, 56

26

Breathable Vapor Toxicant Barriers Based on Multilayer Graphene Oxide

Spitz Steinberg, R1, Cruz, M1, Mahfouz, N1, Qiu, Y1, Hurt, RH1


1Brown University, Providence, RI, USA

There is tremendous interest in the development of ultrathin graphene and graphene oxide (GO) films as molecular transport barriers, or as selective membranes that use molecular sieving properties for small molecular separation or recovery technologies. Graphene oxide films in particular, have been shown to be excellent barriers to transport of small-molecule gases in the dry state, but expand in the presence of water vapor to allow rapid permeation of H2O through nanochannels created in the intersheet gallery spaces. Here we explore a new application for GO films as water-breathable barriers for chemical protection of personnel that allow outward perspiration while protecting the wearer from chemical toxicants or biochemical agents. The interlayer channels in GO films are sufficiently small to exclude larger chemical and biochemical toxicants, but some toxicants are small molecules that can fit in the < 1nm channels, and are known to be co-transported with water. We have developed an experimental facility suitable for the study of vapor permeation in both directions simultaneously, and show results for two model small-molecule vapor agents, trichloroethylene (TCE) and ethanol. We present a theoretical model of small-molecule toxicant diffusion in GO films with motion inward against an outward flow of water to identify conditions where both perspiration and environmental protection can co-exist. The results point to design parameters (film thickness, toxicant properties) that allow both outward water transport and the results suggest that GO can indeed be used to create breathable toxicant barriers as components in wearable devices for chemical and biochemical detection.

27

Carbon Electronics

Silva, S.R.P., Anguita, J., Ahmad, M., Jayawardena, I., Thirimane, H., Kutsarov, D., and, Mills, C.A.


Advanced Technology Institute, University of Surrey, Guildford GU2 7XH, United Kingdom

Carbon as a material can have many faces and phases! It can bond to itself and other elements, creating a plethora of material types. This allows for functionalization of the carbon to produce multi-functional platforms. Better understanding of the synthesis, particularly over a large area, has enabled bottom-up design of nano-carbon films from self-assembled to designer arrays. Coupled with the discoveries of fullerenes, nanotubes and graphene, this has led to a renaissance in the study of carbon as an electronic material. Within this talk we will discuss how large area low temperature growth of carbon nanotubes can be applied to CMOS-type electronic applications, and how this technology can be further extended to the wonder material of the 21st century, graphene. A novel photo-thermal chemical vapour deposition (PT-CVD) route for the CVD growth of nano-carbons including CNT and graphene will be discussed. Further, we examine how different allotropes of nano-carbons can be combined to produce large area solution processable ‘inorganics-in-organics’ hybrid materials suitable for 4th Generation (4G) solar cell devices. Electrical versatility with structural integrity of hybrid nano-carbons opens a new generation of multi-functional materials to be designed with light-matter interactions and large area electronic backplanes for sustainable technologies. The potential for future nano-carbon based electronic devices are numerous and significant, but so are the technical and engineering challenges that need to be overcome. The challenge requires multi-disciplinary teams of scientists and engineers to realise the full potential of this unique material and find solutions to the grand challenges of humanity.

28

Carbon Materials as Catalysts for Microwave Assisted Wet Peroxide Oxidation

Garcia-Costa, A.L., Zazo, J.A., Casas, J.A., Rodriguez, J.J.

[email protected]

Universidad Autonoma de Madrid, Madrid, Spain

In an industrialized world with increasing concern about natural resources, new or intensified wastewater treatment techniques are required. Recently microwave (MW) assisted Advanced Oxidation Processes (AOPs) have gained attention, as this heating method provides higher reaction rates, resulting in an improved energy efficiency in comparison to conventional high temperature processes. Carbon materials present interesting catalytic properties for MW-AOPs. They are MW absorbers and can form hot spots on their surface, which play an important role on MW assisted Catalytic Wet Peroxide Oxidation (MW-CWPO).This work compiles a study of different commercial carbon materials as catalysts for MW-CWPO: carbon black (CB), graphite (G), activated carbon (AC), carbon nanofibers (CNF) and silicon carbide (SiC). Materials were characterized to know their chemical and textural properties. Afterwards catalytic activity was studied in MW-CWPO of a 100 mg·L-1 phenol solution using the stoichiometric dose of H2O2 needed for complete mineralization (500 mg·L-1) with Ccatalyst: 500 mg·L-1, T: 120ºC and pH0 3. Results show a very low activity for CBs and CNF. On the other hand, G is remarkably influenced by chemical properties for both decomposition of H2O2 and mineralization degree. Actually, acidic graphite presents a 7 times higher TOC initial reaction rate than a basic graphite. ACs are the most active materials in MW-CWPO, where an initial high TOC removal suggests a synergy between HOx

• formation and superficial phenomena between intermediates and AC surface. SiC has a middle activity but exhibits a higher H2O2 consumption efficiency in comparison to ACs.

29

Carbon Materials from Conventional/Unconventional Technologies for Electrochemical Energy Storage Devices

González, Z1, Predeanu, G2, Axinte, S3, Fernández, JJ4, Călinescu, I2, Chipurici, P2,

Slăvescu, V2, Drăgoescu, MF3, Acevedo, B5, Melendi-Espina, S5,, Gryglewicz, G6, Menéndez, R1

[email protected]

1 Instituto Nacional del Carbón (INCAR-CSIC, Oviedo, Spain)

2 University Politechnica of Bucharest, Bucharest, Romania 3 Claudiu Top Rom SRL, Bucharest, Romania

4 Química del Nalón SA, Oviedo, Spain 5 University of East Anglia, Norwick, United Kingdom

6 Wroclaw University of Technology, Wroclaw, Poland

In the last years our society has shown a growing interest on the development of both new sources of clean energy and advanced devices able to store it. In this context supercapacitors (SCs) and hybrid systems have emerged to cover the power and energy demands. Most of these electrochemical devices use carbon materials as electrodes being the activated carbons (ACs) the most commonly ones. Nonetheless graphene (G) has emerged as a promising electrode either by itself or combined with ACs in composites. This work investigates the use of a low added value coal-derived liquid (anthracene oil, AO) for the production of pitch-like carbon precursors to synthesize suitable active electrode materials (ACs, G, AC/G) in SCs and hybrid systems. In addition to the well-known oxidative thermal polymerization of AO, a new alternative based on the use of microwave heating is presented as a promising clean route to obtain such carbon precursors resulting in energy saving, shortening time and specific non-thermal effects. The characteristics of the carbon materials obtained from both conventional/ unconventional technologies are compared mainly in terms of their specific surface area, surface chemistry and electrical conductivity which would allow the design of energy storage devices with an improved electrochemical performance. Acknowledgments The research leading to these results has received funding from the European Union’s Research Fund for Coal and Steel (RFCS) research programme under grant agreement RFCR-CT-2015-00006

30

Carbon Nanotube / PVA Composite Aerogels for CO2 Capture

Gromov, A.V.1, Kulur, A.1, Mangano, E.2, Brandani, S.2, Campbell, E.E.B.1


1 School of Chemistry, University of Edinburgh, Edinburgh EH9 3FJ, U.K. 2 School of Engineering, University of Edinburgh, Edinburgh EH9 3FB, U.K.

The key challenge in post-combustion capture of CO2 from gas-fired power plants or other industrial sources is related to the low CO2 concentration in the flue gas (ca. 4−8% by volume). This means that conventional amine processes will result in a relatively high energy penalty, whereas novel adsorbents and adsorption processes have the potential to improve the efficiency of separation. High-selectivity adsorbents are required to achieve relatively high CO2 uptake at low partial pressures. We are developing new materials that combine the practical advantages of solid state absorbents with the high selectivity of liquid amines. A range of porous carbon materials impregnated with liquid amines have been investigated for their CO2 capture behaviour. The most promising results have been obtained with highly porous carbon aerogels that are formed from carbon nanotube (CNT) /polyvinyl alcohol (PVA) composite material. The carbon nanotubes modify the mechanical properties of the aerogel matrix material and also provide materials that are electrically conducting. This allows the development of a capture scheme that involves the use of electric swing adsorption as a means of regenerating materials with high selectivity towards CO2, correlating with high binding energies. The properties of these CNT/PVA aerogels will be described and the effect of processing conditions on these properties. The dependence of CO2 uptake and the kinetics of the capture/regeneration process on the aerogel properties and the material of impregnation will be discussed. We show that such impregnated aerogels with CO2 uptake capacity of > 3 mmol/g are highly promising materials to be incorporated in practical carbon capture schemes.

31

Carbon Nanotube Reinforced Carbon/Carbon Composites with Excellent Mechanical Performance

Hejun Li, Qiang Song, Kezhi Li, Qiangang Fu, Lehua Qi

C/C Composites Research Center, Key Laboratory of Ultrahigh Temperature Composites, Northwestern Polytechnical University, Xi’an Shaanxi 710072, PR China


The introduction of carbon nanotubes (CNTs) into conventional carbon/carbon composites (C/Cs) creates a multiscale reinforcement structure and can significantly improve composite performance. This work reviews the progress to date towards the creation of CNT reinforced C/Cs (CNT-C/Cs) and assesses the effects of CNTs on the microstructures and mechanical prosperities of C/Cs based on the controllable in-situ growth methods. Along with a comparison of the measured improvements in matrix-dominated mechanical properties, CNTs with optimized morphologies, i.e. radially-straight CNTs and aligned CNTs, were obtained, which can increase the compressive and interlaminar shearing strengths of C/Cs by 200~270 %. However, the direct growth of CNTs on carbon fibers has decreased the fiber-dominated properties of CNT-C/Cs due to the surface structure damage of carbon fibers occurred during CNT growth and the overly reinforced bonding betweet carbon fiber and carbon matrix. Towards the excellent global properties of CNT-C/Cs, it is neccessary to fabricate a laminar-structured interface between carbon fiber and CNTs, such as high-textured pyrocarbon and graphene, which can improve the in-situ mechanical properties of carbon fibers and promote their roles as primary reinforcements. Another aspect is to discuss the variety of reinforcing mechanisms according to the SEM observation and micro-indentation tests. It is found that, not only traditional “CNT reinforcing mechanisms” such as CNT pull-out and CNT bridging can be observed, but some new ones such as “microstructure reinforcing mechanisms” that are related to the microstructure improvements of carbon matrix after CNT introduction have been revealed, which obviously increases the cohesion and changes the failure mode of the composites.

32

Carbon Nanotubes/Nickel Hydroxide Composite Electrodes for Electrochemical Capacitors

Smagulova, G,1,2, Hori, K4, Kuzuhara, S4, Prikhodko, N1,3, Lesbayev, B1,2, Noda, S4,

Mansurov, Z1,2

[email protected]

1Institute of Combustion Problems, Almaty, Kazakhstan 2Al-Farabi Kazakh National University, Almaty, Kazakhstan

3Almaty University of Energetics and Communications, Almaty, Kazakhstan 4WASEDA University, Tokyo, Japan

Energy storage systems are the most rapidly developing areas in nanotechnology field. With the development and achieving of nanotechnology and new nanomaterials there is related the opportunities of new methods for generation and storage of energy with sharp expansion of operating parameters range. Among the various nanomaterials and due to filling of electron shells of the atom becomes clear that carbon nanomaterials have taken one of the leading places among the promising nanomaterials. Nickel hydroxide (Ni(OH)2) is a hopeful material to increase the capacity of pseudocapacitors. In this work, nickel hydroxide (Ni(OH)2) - multiwalled carbon nanotube composites for supercapacitor applications were investigated. The composites of Ni(OH)2/CNT are prepared using a electrodeposition method. Electrodeposition was carried out in accordance with three different conditions: CPED – constant potential electrodeposition, CCED – constant current electrodeposition, PED – pulsed electrodeposition. For electrodeposition process under constant potential the best results of gravimetric capacity was from 135 to 73 F/g at scan rate from 5 to 100 mV/s. The studies of electrodeposition process Ni(OH)2 under conditions of constant current showed the results of gravimetric capacitance from 224 to 108 F/g at scan rate from 5 to 100 mV/s, respectively. Experiments with pulsed electrodeposition showed the best results where the gravimetric capacitance for electrode material ranged from 953.5 to 418.9 F/g at allocation from 5 to 100 mV/s, respectively.

33

Carbon Science Development at Morgan Advanced Materials

Armstrong, P.; Buckles, G.; Chavda, M.; Clark, R.; Goshe, A.; Murray, M.

[email protected]

Morgan Advanced Materials, University Park, USA

During CARBON 2016, Morgan Advanced Materials and Pennsylvania State University announced a unique partnership in the carbon science field through the establishment of a Centre of Excellence (COE) in Penn State’s Innovation Park. The intent of the COE is drive global developments in the field of carbon research to support Morgan’s core materials and application engineering activities. The Centre leverages Penn State’s world-class carbon science expertise and materials characterization capabilities, while supporting its role as a leading public research institution. In this presentation, progress toward establishing the COE facility and team at the Innovation Park will be discussed, near-term and long-term execution plans will be presented, and opportunities for collaboration with the carbon science community-at-large will be outlined. The COE will expand and leverage Morgan’s unique expertise in graphitic carbon materials for electrical and mechanical applications, while enabling growth and broadening of its portfolio as global developments in carbon science advance. As an example of Morgan’s collaborative efforts worldwide, work with the National Graphene Institute at the University of Manchester will be described. Morgan and U. of Manchester have been co-developing graphene-related science for over two decades. Recent work has focused on electrochemical routes toward graphite exfoliation and scale-up of the graphene production process. Results from low and high temperature process trials will be discussed in conjunction with efforts to characterize the exfoliated products.

34

Carbon Spheres with Onion-Like Structure as An Anode for Lib

Bin Cao, Huaihe Song,* and Xiaohong Chen Presenting author’s e-mail: [email protected]

State Key Laboratory of Chemical Resource Engineering, Beijing Key Laboratory of

Electrochemical Process and Technology for Materials, Beijing University of Chemical Technology, Beijing 100029, China.

The wide applications of Li-ion batteries promote researchers to find new electrode materials that can satisfy both high energy density and long term cycles for various electronic devices. So far, carbon material with graphitized structure, such as artificial graphite and natural graphite, are main commercial anode materials of Li-ion batteries. There is a great requirement for developing an advanced carbon anode material instead of conventional graphite-based materials from suffering capacity decrease. In this study, we found that graphitized carbon spheres (GCS) with an onion-like structure can have higher capacity of 310 mAh g-1 at 30 mA g-1. Our results show that the onion-like structure can reduce the anisotropy of GCS and thus effectively prevent the interlayer slip or interlayer exfoliation to avoid structural degradation. Benefiting from this structural characteristic, GCS present unexpected superior long-term durability as an anode material for Li-ion batteries.

35

Carbon–Cenosphere Lightweight Composites Foams for High Performance Electromagnetic Interference Shielding

Kumar Rajeev* and Mondal D.P.

Light Weight Metallic Materials Division,

CSIR-Advanced Materials and Processes Research Institute, Bhopal-462026, India

*Corresponding/ presenting author Email: [email protected]

In this study, the high-performance carbon-cenosphere lightweight composite foam was developed by using a simple sacrificial template technique from a mixture of cenosphere particles (-100µm) and phenol formaldehyde resin as a carbon source. The developed light weight composite foam have superior specific electromagnetic interference (EMI) shielding -142 dB.cm3/g in X-band (8.2-12.4 GHz) frequency region having a low density of 0.35 g/cm3. The carbon-cenosphere composites foam with cenosphere loading of 30 wt. % significantly increases the interfacial polarization and anisotropy energy of the composite foam which leads to an excellent absorption dominated EMI shielding effectiveness (SE) of -42.9 dB at a thickness of 2.5 mm. However, the compressive strength of carbon foam improved by 24.1 % (7.8 MPa) by the incorporation of 10 wt. % cenosphere particles in a carbon matrix. The composite foam also exhibits improved dielectric properties and thermal stability that increase on increasing the concentration of cenosphere particles. This technique is very fast, highly reproducible, and scalable, which may facilitate the commercialization of such composite foam and it can be used as EMI shielding materials in the fields of aerospace applications where light lightweight materials are required.

36

Carbon paper prepared from nanoporous carbon fibers using HyperCoal through an electrospinning technique and its characteristics

Toyoda, M*1, Ohtani, Y1, Hamaguchi, M2, Wada, S2, Inoue, T3, Kinumoto, T1, Tsumura, T1,


1 Faculty of Engineering, Oita University, Oita, Japan.

2 Kobe Steel, Ltd., Kobe, Japan. 3 Kobelco Research Institute Inc., Kobe, Japan.

Nanoporous carbon has attracted considerable attention in recent years owing to its numerous unique characteristics, such as extremely large adsorption capability and high selectivity as compared to those of conventional activated carbons. To obtain nanoporous carbons, so-called “template materials” such as metal oxides are usually employed to tailor the porous carbon structure. However, these template methods are complicated and involve expensive processes from an industrial viewpoint. For the first time, this research reports a simple template-free method for synthesizing nanoporous carbon via electrospinning of a coal extract. HyperCoal (HPC) is an ash-free and thermoplastic material prepared via high-temperature extraction of coal with a methylnaphthalene-based solvent. In this study, a carbon paper prepared from porous microcarbon fibers using HPC was studied. A concentrated HPC solution (approximately 35 wt%) in pyridine was continuously electrospun into microfibers with a diameter ranging from a few micrometers to submicrons. The as-obtained precursor fibers were converted into microcarbon fibers and paper without fusion or sticking by heat treating under an inert atmosphere. Microcarbon fibers or paper prepared from HPC via electrospinning and carbonized at 900 °C surprisingly exhibited high specific surface areas exceeding 1000 m2/g without any activating treatment. Electric double-layer capacitors (EDLCs) were fabricated using the microcarbon fibers derived from HPC as electrodes, and their properties were evaluated in an aqueous electrolytic media. The EDLC device containing HPC microcarbon fibers possessed a stable charge–discharge performance with a capacitance as high as 400 F/g.

37

CF4 Adsorption on Carbide-Derived Microporous Carbon

Choi, SW1, Lee, D-H2, Lee, H-J2, Beum, HT3, Park, J-H3, Kim, J1, Kim, J1, Lim, D-S2, Lee, KB1


1 Department of Chemical and Biological Engineering, Korea University, Seoul, Republic of Korea

2 Department of Materials Science and Engineering, Korea University, Seoul, Republic of Korea

3 Oil and Gas Center, Korea Institute of Energy Research, Daejeon, Republic of Korea

Various urgent environmental problems are attributed to the global warming, and there are many different greenhouse gases causing global warming. Based on the same mass, the ratio of heat trapped by certain greenhouse gas to that trapped by carbon dioxide is quantitatively expressed as the global warming potential (GWP). Tetrafluoromethane (CF4) has a large GWP value of 7,390 and extremely long atmospheric lifetime of 50,000 years. CF4 is usually used for etching processes in manufacturing of semiconductor. Recently, the usage of fluorinated gases such as CF4 has largely increased due to the rapid growth of semiconductor industry, therefore CF4 capture should be considered for mitigating global warming. CF4 is currently disposed by plasma combustion. However, it requires lots of energy and produces toxic gases. Adsorption can be an alternative technique because it has many merits of convenient operation, relatively low cost, and easy scale-up. For a competent CF4 adsorption process, the development of appropriate adsorbents is important. In this study, microporous carbon was synthesized for a new CF4 adsorbent by selective etching of carbide using chlorine gas at high temperature of 800, 900, and 1000 °C. Hydrogen was additionally used to eliminate unreacted chlorine which remained in carbide-derived carbon material. Because of the regular lattice structure of carbide precursor, the obtained carbon had narrow pore size distribution. The carbide-derived carbon showed high CF4 adsorption uptake at ambient pressure and temperature, high selectivity of CF4 over N2, and excellent cyclic adsorption-desorption stability, which implies practical applicability of this adsorbent.

38

Characterization Of C/C Composite Fabricated By Film Boiling Technique

Iwashita, N1, Soneda, Y1, Uda, M2, Yamauchi, H2


1 National Institute of Advanced Industrial Science and Technology, AIST, Tsukuba, Ibaraki, Japan

2 IHI Aerospace, Tomioka, Gumma, Japan

Carbon fiber reinforced carbon matrix composite (C/C composite) has been fabricated by a new technique by film boiling (FB) method. 0/90 laminated carbon fiber sheets were used as preform for C/C composites. In-layer between carbon fiber sheets, needle-punched carbon fiber felt was located. The carbon fiber preform immersed in cyclohexane was heat-treated at 1100-1200 for 2 days (6hrs and 7hrs). The carbon matrix was piled up carbon fiber surrounding by pyrolysis of cyclohexane vapor. Bulk density of the fabricated composite was 1.70-1.78 g/cm3. Four-point bending test of the C/C composite fabricated by FB technique was carried out at different temperatures from ambient to 2400 . Morphologies of the fractured composites and of the heat-treated carbon matrix texture were investigated under SEM

39

Chemically Derived Graphene: From Scale-Up Production to Multifunctional Applications

Cheng-Meng Chen1, Qing-Qiang Kong1, Fang-Yuan Su1, Li-Jing Xie1, Xiao-Ming Li1


1 Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, China

Since 2014, we achieved the scale-up production of graphene powder by Hummers’ oxidation-thermal reduction method, with capability of 1 ton/year in our pilot plant. In this process, several challenges on chemical engineering and particle processing of the two-dimensional carbon material was overwhelmed. The as-produced graphenes are of high quality, with BET surface area of >500 m2/g and ash content of <0.1 wt%, while the cost was reduced to <1 $/g. One the basis, the exploitation for industrial application become a challenge for the sustainable development of graphene. On one hand, as the conductive additives, graphene was employed to activated carbon for supercapacitor electrode. The paste rheology and component compatibility were systematically studied, so as to realize the ultimate use of graphene property in a real device. Both the graphene modified coiling and laminate type supercapacitor showed improved energy and power density. At the same time, some asymmetric devices based on graphene/metal oxide hybrids and porous carbon electrode, were also designed. On the other hand, in order to make the fluffy graphene more accessible to industrial application, it is a good strategy to fabricate the shaped functional materials by nanoscale dispersion or macroscopic assembly. Herein, we produced various graphene based ink, polymer or ceramics, which show remarkable enhancement in conductive and/or mechanical performance. Besides, the macroscopic assemblies such as graphene/carbon fiber hybrid film for lateral heat spreader was prepared, which showed high in-plane thermal conductivity of >1000 W/m.K. The above work provided fundamental and insight for the industrialization of chemically derived graphene.

40

Co@S,N-doped hydrothermal carbon: sacrificial electrode for water splitting

Ding, Y1, Buller, S1, Schlögl, R1,2


1Max Plank Institute for Chemical Energy Conversion, Mülheim an der Ruhr, Germany 2Fritz Haber Institute of the Max Planck Society, Berlin, Germany

The development of efficient, stable and low cost water oxidation catalysts continues to be centrally important to the conversion of light energy into chemical energy.[1-2] Carbon is believed as a very stable catalyst or support for water splitting in many cases and the electrochemical stability of carbon is rarely considered. In the current work, we found out that carbon can be oxidized from some defect sites during oxygen evolution reaction (OER). Hydrothermal carbons (HTCs) with different graphitic structures and heteroatoms are synthesized to find out the oxidation mechanism of carbon defects. Additionally, the introduced cobalt species in the carbon structure are not only active for the OER reaction, but also active for the HTC oxidation. Due to the low cost of the HTC, the as-synthesized Co@N,S-doped HTC can be used as a sacrificial anode for water splitting, thus providing a different way to produce hydrogen on the counter electrode. [1] R. Eisenberg, H. B. Gray, Inorg. Chem. 2008, 47, 1697-1699; [2] N. S. Lewis, D. G. Nocera, Proc. Natl. Acad. Sci. U. S. A. 2006, 103, 15729-15735.

41

Compact energy storage: Opportunities and challenges of graphene for supercapacitors

Ying Tao1, Huan Li1, Yue Xu1, Quan-Hong Yang1,2


1 School of Chemical Engineering and Technology, Tianjin University, Tianjin, China 2Tsinghua-Berkeley Shenzhen Institute (TBSI), Tsinghua University, Shenzhen, China

Gravimetric energy densities of nanocarbons continuously improved over the years. However, due to their low densities, these nanomaterials normally suffer from relatively low volumetric performance, and their high gravimetric performance also cannot be realized to the practical devices. Developing electrode materials with high volumetric performance and achieving compact energy storage on a device level is highly important to promote the materials and devices for energy storage into real applications. As a basic unit for all types of sp2 carbons and flexible 2D material, graphene has many intrinsic characteristics beneficial to compact energy storage. Based on the applications of graphene in supercapacitors, the report will presents design principles for practical energy storage devices from the perspective of material, electrode and devices respectively. The recent efforts to prepare electrode materials with a high volumetric performance, particularly the design concept on the high density electrode materials for high volumetric performance are also introduced. The report further highlights the importance to design energy storage material from a device perspective and discusses the opportunities and challenges of graphene toward compact energy storage.

42

Confirmation of The Formation of Oxidative Debris During the Hummers-Offeman

Reaction in The Synthesis of Graphene Oxide

Ramos-Fernández G.1, Domene-López D1., Ortuño, N., Martin-Gullón I.1

[email protected] 1University of Alicante, Alicante, Spain

The structure of graphene oxide (GO) is a matter of discussion. A two-component structural model for GO was proposed as a direct product of the oxidation reaction: slightly oxidized, structurally intact graphene-like sheets (bwGO) and highly oxidized molecular species, oxidative Debris (OD), adsorbed on it, which can be separated by a base digestion. Recently, this model was strongly criticized stating that the debris are formed when producing the base digestion of previously dried graphite oxide and not in the Hummers-Offemann reaction. The present paper determines the amount of bwGO and oxidative debris (including humic and fulvic like fractions), and its spectroscopic and electron microscopy characterization, formed when starting from the Hummers-Offeman reaction, and just after the base digestion was carried out without any intermediate drying of graphite oxide nor sonication treatment. This procedure all wet procedure ensured us to know if the rehydration and alkaline treatment is the responsible of the OD generation. The results show that gravimetric OD and bwGO determined is similar to that quantified when starting from dried graphite oxide. TEM and FESEM indicated that bwGO sheets decomposed into OD the oxidated level of graphite oxide was extreme. We concluded that the OD formation is directly related to the pattern material and the oxidation process employed and does not depend on the subsequent processes such as the ultrasounds or the basic treatments used to separate the OD fraction.

43

Controlled Blocking of The Porosity to Understand Water Sorption Processes

Velasco, LF1, Silvestre-Albero, J2, Thommes, M3, Lodewyckx, P1

[email protected]


2 Inorganic Chemistry Department, University of Alicante, Ap. 99, E-03080 Alicante, Spain 3 Quantachrome Instruments, 1900 Corporate Drive, Boynton Beach, FL 33426, USA

Recently, appreciable progress has been made in understanding the mechanisms of water adsorption in nanoporous carbons, but still open questions remain for activated carbon materials consisting of complex pore networks of micro- and narrow mesopores. Specifically,more work is needed to understand the details of the water pore filling mechanism into the narrow mesopores of activated carbons Moreover, and besides the specific interactions taking place at the first stages of the water sorption process, it is still necessary to correlate the differentiated parts of the water isotherm with the filling of pores of a given pore size. To attain this goal, several activated carbons showing a progressive widening of the pore size distribution were chosen for this study. The samples were further preloaded with an n-alkane in order to gradually fill their micropore system. Subsequently, a thorough textural characterization was performed by means of N2, CO2 and H2O isotherms before and after the preadsorption step. Finally, water scanning isotherms were measured on the preloaded samples. The controlled blockage of the pores with the n-alkane made possible to correlate the changes in the shape of the water isotherm with the couple N2 and CO2 pore size distributions. The results obtained by this approach not only allow us to better understand the mechanisms of water adsorption in carbon pores in terms of their size, but also to evaluate the differences found in the micropore volumes given by different adsorbates.

45

Controlled CVD Growth and Optoelectronic Applications of Graphene Films

Wencai Ren


Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, P.R. China

Controlled growth of graphene films at a low cost by chemical vapour deposition (CVD)

is essentially important for their applications in electronics and optoelectronics, but it is still very challenging. Here, I will first talk about the growth mechanism of graphene, controlled growth of high-quality millimetre-size single-crystal graphene domains and well-stitched polycrystalline graphene films with tunable uniform grain size, and the influence of grain size on the electrical and thermal transport properties of graphene films. Then I will talk about several critical issues about transfer, an indispensable step for electronic and optoelectronic applications of CVD-grown graphene films on metals, including metal substrate non-destructive transfer, ultraclean and damage-free transfer, improvement on the electrical conductivity and adhesion, and scaling. Finally I will demonstrate the use of CVD-grown graphene films for large-area flexible touch panels and OLEDs. References [1] W.C. Ren, H.M. Cheng, Nature Nanotechnology 9 (2014) 726. [2] L.B. Gao, W.C. Ren, H.M. Cheng, et al., Nature Communications 3 (2012) 699. [3] T. Ma, W.C. Ren, F. Ding, H.M. Cheng, et al, PNAS 110 (2013) 20386. [4] T. Ma, W. C. Ren, H.M. Cheng, et al., ACS Nano 8 (2014) 12806. [5] Y. Gao, H.M. Cheng, W.C. Ren, et al., Nature Communications 6 (2015) 8569. [6] T. Ma, H.M. Cheng, W.C. Ren, et al., Nature Communications Accepted (2017). [7] X. Xin, H.M. Cheng, W.C. Ren, et al., Advanced Materials Accepted (2017). [8] Z.K. Zhang, J.H. Du, H.M. Cheng, W.C. Ren, et al., Nature Communications Accepted (2017).

46

Controlled Folding of Single Crystal Graphene

Bin Wang 1, Rodney S. Ruoff 1, 2


1. Center for Multidimensional Carbon Materials (CMCM), Institute for Basic Science (IBS), Ulsan 44919, Republic of Korea;

2. Department of Chemistry and School of Materials Science and Engineering, Ulsan National Institute of Science and Technology (UNIST), Ulsan 44919, Republic of Korea.

Folded graphene in which two layers are stacked with a twist angle between them has been predicted to exhibit unique electronic, thermal, and magnetic properties. We report the folding of a single crystal monolayer graphene film grown on a Cu (111) substrate by using a tailored substrate having a hydrophobic region and a hydrophilic region. Controlled film delamination from the hydrophilic region was used to prepare macroscopic folded graphene with good uniformity on the millimeter scale. This process was used to create many folded sheets each with a defined twist angle between the two sheets. This folding technique allows for the preparation of twisted bilayer graphene films with defined stacking orientations and may also be extended to create folded structures of other two dimensional nanomaterials.

47

Conversion of Kerosene to Carbon Nanotubes Via Co-Pyrolysis With Ferrocene

Chaiwat, W1, Thonganantakul, O2, Vaewhongs, P2, Charinpanitkul, T2, Suttiponparnit, K3


1 Environmental Engineering and Disaster Management Program, School of Interdisciplinary Studies, Kanchanaburi Campus,

Mahidol University, Kanchanaburi, Thailand

2 Center of Excellence in Particle Technology, Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn University, Bangkok, Thailand

3 Environmental Technology Research Department, PTT Research and Technology Institute, Ayutthaya, Thailand

Kesosene which is a representative of light distillates fractionated from slop oil or liquid hydrocarbon waste from petroleum refinery has a potential as carbon source for mass production of carbon nanotubes (CNTs). Ferrocene was employed as additional carbon and Fe catalyst source. Two portions of ferrocene were separately supplied into a quartz tube reactor for synthesis of CNTs. The 1st portion of ferrocene in a ceramic boat (F1) was vaporized by heating up to 550°C under a nitrogen gas flow of 100 cc/min. The 2nd portion (F2) was completely mixed with kerosene in prior to being fed continuously into the reactor with a flow rate of 3 cc/min. All carbon sources were decomposed and underwent the self-assembly process of CNTs within the reaction zone at elevated temperature in a range of 800-1000 C. The weight ratio of total ferrocene (F1+F2) and kerosene (K) or Ftotal:K was varied from 1:5 to 1:20. In addition, the ratio of ferrocene portion (F1:F2) was also changed for investigating the role of ferrocene in initiating the formation of CNTs. SEM images of synthesized products showed bundles of long and curly CNTs with a diameter of 20-100 nm. The highest carbon yield over 50 wt% of CNTs could be achieved at 900°C with the Ftotal:K ratio of 1:5. It is interesting that the 1st portion of ferrocene (F1) significantly contributed to an increase in CNT yields.

48

Correlations the Atomic Structure‒Mechanical Properties for Glass-Like Carbons

Jurkiewicz, K1,2, Duber, S1, Pawlyta, M3, Chrobak, D1,2, Fischer, HE4, Burian, A1,2

[email protected]

1 University of Silesia, Katowice, Poland 2 Silesian Centre for Education and Interdisciplinary Research, Chorzów, Poland

3 Silesian University of Technology, Gliwice, Poland 4 Institute Laue-Langevin, Grenoble, France

Glassy carbon is a class of non-graphitizing, nanoporous, disordered carbon primarily consisting of sp2-hybridized carbon atoms. Its Young's modulus of 20-40 GPa is about ten times higher than that of crosslinked epoxy resins and its hardness up to 6 GPa is comparable to that of silicate glasses. It has recently been shown that the glassy carbon can be used to produce ultra-strong nanolattices achieving strength-to-density ratios which markedly exceed those of all cellular solids [1]. The basic physical relationships between nano-scale structural variables and the macroscale properties of glassy carbon remain unexplained in details. An open question is the origin of its high hardness and strength. Here we try to establish the structure-properties correlations of a series of glass-like carbons produced by pyrolysis of polyfurfuryl alcohol. Given the complexity of glassy carbons atomic arrangement and their sensitivity to the synthesis temperature we used characterization based on the molecular dynamic simulations of structure and their experimental verification by the wide-angle X-ray and neutron scattering. The applied pair distribution function analysis showed that the glassy carbons have local order extending on the length scale of tens of angstroms, in which carbon atoms are arranged in fullerene-related, curved units. The results of the structural modelling suggested that the curvature can arise from the presence of defects in the form of nonhexagonal carbon rings. In consequence, the combined studies bring new models of glassy carbon atomic structure that can explain the origin of its properties [2]. [1] Bauer, J., Schroer, A., Schwaiger, R., & Kraft, O. (2016). Approaching theoretical strength in glassy carbon nanolattices. Nature materials, 15. [2] Jurkiewicz, K., Duber, S., Fischer, H. E., & Burian, A. (2017). Modelling of glass-like carbon structure and its experimental verification by neutron and X-ray diffraction. Journal of Applied Crystallography, 50(1).

49

Corrugated graphitic layers catalysing oxygen reduction reaction

Jun-ichi Ozaki1, Naokatsu Kannari1, Kumi Nariduka1, Takuya Maie1, Koji Takasu1, Takafumi Ishii1, Machiko Takigami1


1 Gunma University, Kiryu, Japan

Carbon based catalysts receive attentions as possible alternatives of platinum based catalysts for oxygen reduction reaction (ORR) in polymer electrolyte fuel cells. Two major candidates of the active sites of these catalysts are discussed to be the metal (Fe or Co) complexes coordinated to nitrogen atoms embedded on the carbon surfaces and the graphitic layers modified by the nitrogen doping. In this presentation, we will report the possibility of the corrugated graphitic layers (CGL) as a factor to determine the ORR activity of the carbon-based catalysts by comparing the properties of the carbon catalysts that we have studied. Firstly, the possibility will be exemplified by a study on the nanoshell-containing carbon (NSCC). Purification of nanoshell structure (NS) from NSCC by removing the amorphous moiety formed in the NSCC resulted in the increased ORR activity and the exposure of CGLs formed on the NS surfaces. A removal of the CGLs from the purified NS by a heat-treatment at 1500°C resulted in deterioration of the ORR activity of NS. These observations suggested the importance of the CGLs in ORR. The ORR activity of such structures prepared from different methods also supported this hypothesis. Finally, we conducted kinetic studies to understand the impacts of the CGLs on the elementary steps in ORR.

50

Crystallographic Microstructure Investigation in Pan-Based Carbon Fibre by Synchrotron Micro-Waxs

Creighton, C1, Lynch, P1 2, Nunna, S1, De Jonge, M3, Mudie, S3, Fox, B4


1Carbon Nexus, Institute for Frontier Materials, Deakin University, Geelong, Australia 2 CSIRO, Manufacturing Flagship, Geelong, Australia

3 Australian Synchrotron, 800 Blackburn Rd, Clayton, Victoria, Australia 4 Factory of the Future, Swinburne University, Hawthorn, Victoria, Australia

It is well understood that the orientation distribution of the microcrystallites in Polyacrylonitrile (PAN) based carbon fibre plays a leading role in controlling the fibre’s strength and modulus. By application of a synchrotron micro-focus X-ray source (X-ray probe size ~1.5 μm2) the crystallographic heterogeneity of single PAN precursor and the subsequent carbon fibre processed using the 110 ton carbon fibre pilot line (Carbon Nexus, Deakin University) is measured. As fibre monofilaments are raster scanned (1μm step increment) across the highly focussed incident X-ray probe Wide Angle X-ray scattering (WAXS) patterns are recorded using a 2D Pilatus detector. By recording the (100) and (002) WAXS patterns for the PAN and carbon fibres respectively, the fibre crystallographic orientation was measured at the beginning and the end of the carbon fibre manufacturing process. Azimuthal measurements showed the initial PAN orientation within the fibre core was 30.5o which increased to 31.8o near the edges. While the carbon fibre showed a similar trend, at the core the orientation spread was 29.8o and at the skin 31.7o. These results confirm the initial crystallographic orientation and heterogeneity observed in the PAN precursor fibre is retained during carbon fibre processing path.

51

Curved And N-Doped Carbon Nanostructures Obtained by Salt Melt Synthesis

Rybarczyk, M.K.1, Lieder, M1


1 Chemical Faculty, Department of Chemical Technology, Gdansk University of Technology,

11/12 Narutowicza St., 80-233 Gdansk, Poland

Chitosan is an N-deacetylated product of chitin, which is the second most abundant natural polymer (after cellulose) and can be successfully utilized as nanocarbons precursor for energy conversion and storage purposes. In this study, we have shown that the direct carbonisation of low cost and abundand chitosan biopolymer in the presence of salt leads to 1D curved graphene nanostructures with a high onset potential and an increased turnover frequency (TOF) of catalytic sites for oxygen reduction. The catalytic activity is enhanced due to the curved morphology of the carbonaceous matrix, which exposes the reactive sites to the oxygen reagent. This is the first report on showing the formation of curved graphene layers and carbon nanotubes received from a biopolymer precursor which induces unexpected deformation in the grown graphitic layers. Further, the used salts allow to preserve the nitrogen content to ca. 8%, which is located solely at the edges of the carbon matrix. We postulate that the improved catalytic performance of the synthesised material can be attributed to the pyridinic and pyrrolic sites. The electrochemical studies show, that this novel material is highly active towards four-electron pathway of the ORR in terms of an onset potential (0.89 V vs RHE) and the turnover frequency (TOFmax = 0.095 e site-1 s-1). These graphene layers are composed of a stack of 5-10 sheets, which are turbostratic.

52

Defect Engineering of Graphene and Other 2d Materials

Ruitao Lv1*, Feiyu Kang1, Mauricio Terrones2


1Key Laboratory of Advanced Materials (MOE), School of Materials Science and Engineering, Tsinghua University, Beijing, 100084, China

2Department of Physics, The Pennsylvania State University, University Park, PA 16802, USA

Defects are usually regarded as imperfections in materials that could significantly degrade their performance. However, at the nanoscale, defects (e.g. dopants, vacancies) can be exploited to generate novel and useful materials and devices. Therefore, defect engineering of 2D materials is becoming an important research line so far. In particular, substitutional doping with heteroatoms is a very efficient way to tailor the electrical and chemical properties of graphene. Both experimental and theoretical research on N-doped graphene have been extensively carried out. However, the experimental reports on large-area Si-doped and B-doped graphene sheets are still quite few so far. In this contribution, we summarize our recent progress on controllable synthesis of centimeter size, high-crystallinity doped graphene sheets [1,2]. Their excellent sensing properties are demonstrated by using gaseous (e.g. NO2, NH3) and liquid molecules (e.g. crystal violet, rhodamine B and methylene blue) as probes [1,2]. Besides graphene, other 2D layered materials (e.g. transition metal dichalcogenides, TMDs) are attracting worldwide research attentions [3]. We also demonstrated the defect engineering of TMDs for ultrasensitive pressure sensing [4] and highly efficient hydrogen evolution reaction (HER) catalysis [5]. Our results will open up new avenues for developing high-performance sensors and generating clean energy with 2D materials.

References [1] R. Lv*, et al. Adv. Mater., 26: 7593-7599 (2014) (Back Cover) [2] R. Lv, et al. PNAS, 112: 14527-14532 (2015) [3] R. Lv, et al. Acc. Chem. Res., 48: 56-64 (2015) (Front Cover) [4] R. Lv*, et al. Adv. Mater., DOI: 10.1002/adma.201603266 (2016) (Inside Cover) [5] R. Lv*, et al. Adv. Mater., DOI: 10.1002/adma.201603617 (2016)

53

Defective graphene as catalysts for electrochemical ammonia synthesis

Qinye Li1, Chenghua Sun2, Xiwang Zhang1

[email protected]

1School of Chemistry, Monash University, Clayton, VIC 3800, Australia 2Department of Chemistry and Biotechnology, Faculty of Science, Engineering and Technology, Swinburne University of Technology, Hawthorn, VIC 3122, Australia

Surface defects, after the distortion from the perfect structure, often offer novel properties. For instance, topological defects (TDs) are found to show excellent catalysis performance for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). In this work, experimental study and theoretical calculation have been performed to investigate the effect of TDs (5775 and 585 defects) on the catalysis for electrochemical synthesis of ammonia at room temperature. We found that TDs can effectively promote N2 adsorption and activation, but pure carbon framework has strong adsorption on NH-NH species. Doping approaches have been further identified after computational screening to improve this. In-spired by the computational modelling, laser-based surface modification has been employed to validate the prediction.

54

Design Principles of Heteroatom-Doped Graphene Catalysts for Dye-Sensitized Solar Cells

Zhenghang Zhao and Zhenhai Xia


Department of Materials Science and Engineering, University of North Texas, Denton, TX

76203, USA

Doped carbon nanomaterials are promising candidates to replace expensive Pt counter electrode for catalyzing triiodide reduction reaction (TRR) in dye-sensitized solar cells (DSSCs), but trial-and-error approaches have been used to develop better carbon-based catalysts. Here, design principles are developed for p-block heteroatom-doped graphene as metal-free TRR catalysts through density functional theory (DFT) calculations. Descriptors relating intrinsic properties of dopant elements are identified to establish a volcano relationship that correlates the doped structures to the catalytic activities of the carbon-based catalysts. It is predicted that dopants, such as P, O, S and Se, near summit of the volcano have their performance comparable or higher than that of Pt, and that the graphene hetero-edges facilitate the reactions. These predictions are consistent with experiments. The principles enable us to rationally design and search for highly active catalysts based on earth-abundant, cost-effective materials

55

Designing the carbon/vanadia interface for hybrid electrochemical energy storage

Zeiger, M1,2, Fleischmann, S1,2, Etzold, J M B3, Presser, V1,2


1 INM - Leibniz Institute for New Materials, 66123 Saarbrücken, Germany

2 Department of Materials Science and Engineering, Saarland University, 66123 Saarbrücken, Germany

3Technische Universität Darmstadt, Ernst-Berl-Institut für Technische und Makromolekulare Chemie, 64287 Darmstadt, Germany

Carbon nanomaterials have gained widespread utilization in the field of energy storage, especially for supercapacitors. Yet, the specific energy of supercapacitors remains small compared to batteries, so that carbon hybridization with metal oxides has been explored.[1] In such systems, the metal oxide provides a large specific energy, while nanocarbons enable a large interface with high conductivity. In our studies, we extracted three key findings for hybrids of vanadia with carbon using different material architectures. Carbons without inner porosity are to be preferred. First, when using vanadia coatings on carbon, carbons with inner porosity show unwanted pore blocking. Instead, the interparticle porosity of carbon onions (5-10 nm diameter) remained unaffected by the metal oxide coating.[2] Their hybridization with vanadia results in enhanced rate handling with 53 % capacity retention (initial value: 129 mAh/g) at 5 A/g, which is far superior to the performance of vanadia-coated activated carbon.[3] The carbon surface termination influences the metal oxide coating. Second, a more homogenous coating process with high vanadia loadings was achieved by a pre-activation process of the carbon onion substrate. Annealing in synthetic air covers the carbon nanoparticles with oxygen-containing functional groups, which work as nucleation centres for sol-gel-derived vanadia. Nanoporous carbon engulfing metal oxide domains allows high power. Vanadium carbide was converted to carbon shell / vanadia core hybrid material. The resulting electrodes enabled more than 80 Wh/kg specific energy and 10 kW/kg specific power in asymmetric full cells.[4] This was enabled by the improved ion accessibility provided by the porous carbon shells.

1. Béguin, F., et al., Advanced Materials, 2014. 26(14): p. 2219-2251. 2. Zeiger, M., et al., Journal of Materials Chemistry A, 2016. 4: p. 3172-3196. 3. Fleischmann, S., et al., Chemistry of Materials, 2016. 28(8): p. 2802-2813. 4. Zeiger, M., et al., Journal of Materials Chemistry A, 2016. 4(48): p. 18899-18909.

56

Developments and Opportunities in Nanocomposites and Functional Fibers Kumar, S

[email protected]

Georgia Institute of Technology, Atlanta GA

A In this presentation, we will briefly review the developments in the field of functional fibers and nanocomposites over last few decades. We will then discuss recent developments in authors’ laboratory. We have recently shown that by tailoring the interphase in nanocomposite materials, significant property improvements can be obtained. For example, by using the interphase tailoring approach, impact strength of polypropylene has been increased by 150%, by including only 1 wt% carbon nanotubes. The approach used for polypropylene should have broad applicability to other polymers and to other nano materials. In another approach in tailoring the interphase, we have shown that poly(methyl methacrylate) (PMMA) wraps helically in an ordered manner around single wall carbon nanotubes (SWNT). Composite films and bucky papers made using PMMA wrapped SWNTs show significantly higher mechanical properties than without PMMA wrapped films and bucky papers. Significant evidence of load transfer in PMMA wrapped nanotubes, and the absence of load transfer without PMMA wrapping has also been obtained using Raman spectroscopy. The work on functional fibers include polymeric fibers with a range of electrical and thermal conductivity, as well as superparamagnetic properties. Other functionalities can also be included in various fibers. Work is also ongoing to incorporate cellulose nano crystals and lignin in fibers. Incorporation of these biomaterials is driven to enhance product sustainability and to reduce cost. The presentation will also include recent development in scalable and economic route for synthesizing a very high surface area carbon (surface are >3000 m2/g), and for making hollow carbon fiber.

57

Diamond and graphene components as building materials for biomedical implants

Garrett DJ1


1 University of Melbourne, School of Physics, Melbourne, Australia

With the incredible success of cochlear implants for the deaf and rapid advances in retinal implants for the blind, bionics is no longer the stuff of science fiction. For now the majority of applications are in medicine but it is easy to forecast that efforts to integrate electronics with our biology for the purpose of enhancing our physical abilities, for heightening our senses

will not be far behind. A critical challenge is the creation of long lasting, safe interfaces for transfer of information to and from the peripheral or central nervous system. Active neurons produce electrical signals that can be recorded and neurons can be activated by introducing small packets of electrical charge into their immediate vicinity. The “go to” technology for such electrical interfaces is implantable electrode arrays. Our immune systems however are highly evolved to protect us from foreign materials and employ a variety of strategies to either destroy or neutralise the threat. If implantable electrodes are going to be a viable technology for the future of

neuromodulation implants they need to be at least invisible to the immune system but ideally they will work with the immune system to actively generate high fidelity long lasting connections. This talk will introduce some of the research we have conducted (Figure 1) and techniques we have developed pertaining to fabrication of devices from all carbon materials; diamond, graphene, carbon fibre and carbon nanotubes. In the field of retinal prosthesis for instance we used diamond both as an encapsulant for electronic components and as a retinal stimulation interface. More recently we have produced flexible electrodes from graphene and carbon nanotube yarns that show promise as a dual recording and stimulation electrodes. The superior biocompatibility of carbon materials and better mechanical match to living tissue may provide a route towards long lasting implantable electrodes.

Figure 1. Architecture of the eyewall (a), an epiretinal implant (b) and the cellular structure within the retina. (c)

58

Dielectric Behavior of Carbon Materials

Chung, D.D.L.


Composite Materials Research Laboratory, Department of Mechanical and Aerospace Engineering, University at Buffalo,

The State University of New York, Buffalo, NY 14260-4400, U.S.A.

The electrical behavior of a material pertains to the conduction behavior (related to the electrical conductivity, which dictates the electrical resistance) and the dielectric behavior (related to the electric permittivity, which dictates the capacitance). Polarization causes capacitance build-up and thus an increase in the measured DC resistance. Concerning carbon materials, much attention has been given to the former, but little attention has been given to the latter, though both are relevant to the use of carbon materials in batteries, capacitors, and other electrochemical and electrical devices. Applications include electrodes and electrically conductive additives. The relative permittivity of carbon materials varies over a wide range, due to the differences in structure and surface functional groups. For example, its value at 50 Hz ranges from 31 for carbon black to 124 for activated carbon, to 915 for graphite oxide, and to 1130 for reduced graphite oxide. In case of carbon black, which deforms upon compression, the permittivity depends on the deformation, which probably enhances the dielectric connectivity and hence the polarizability. Furthermore, deformation occurs upon compression of carbon black between particles of manganese dioxide, which is a nonconductive active battery electrode material. The presence of a liquid electrolyte enhances the dielectric connectivity and hence the permittivity of the carbon. The through-thickness permittivity of continuous carbon fiber polymer-matrix composites has been tailored by modifying the interlaminar interface, thereby providing structural capacitors. A pitfall due to inadequate recognition of the limitation of an impedance meter has resulted in incorrect reports in the literature.

59

Different strategies for enhancing the neural interaction on diamond surfaces

Tong W.1, Turnley, A.2, Fox, K.3, Prawer, S.1, Garrett, D.1


1 School of Physics, University of Melbourne, Parkville, Australia 2 Department of Anatomy and Neuroscience, University of Melbourne, Parkville, Australia 3 Centre for Additive Manufacturing, School of Engineering, RMIT University, Melbourne,

Australia

Diamond is fast becoming a highly sought after biomaterial for developing neural implants due to its outstanding properties, including biocompatibility, biochemical stability, chemical inertness and mechanical stability. The success of neural implants resides in the intimate contact between neural cells and electrodes that enables long-term safe neural stimulation and high-quality electrophysiological recordings. Therefore, promoting neural growth on diamond surfaces is an effective approach to enhance electrical communication between the cells and the devices and to improve the performance of the diamond neural implants. In this study, two different strategies are proposed to improve the adhesion of neurons and their neurite outgrowth on nitrogen included ultrananocrystalline diamond (N-UNCD) surfaces. The first strategy enhances the neural growth through the optimisation of diamond surface morphology. In vitro rat cortical neuron cultures were grown on N-UNCD surfaces modified with plasma etching. Optimal neuron growth was found to be highly affected by the roughness of the diamond surfaces, with best growth occurring on surfaces with a root-mean-square roughness of ~20 nm. Another strategy involves the functionalization of surfaces with biologically relevant molecules. Biomolecules, such as laminin and fibronectin, have been shown to enhance cell adhesion and neurite outgrowth. Here, we first demonstrate that the adsorption of laminin on diamond surface can significantly improve the growth of neurons. The comparison between adsorption and covalent chemical bonding of laminin on diamond surfaces for neural growth will then be presented.

60

Dynamic Self-Stiffening and Structural Evolutions of Polyacrylonitrile/Carbon Nanotube Nanocomposites

Li, Y; Liu, Y; Lu, C


National Engineering Laboratory for Carbon Fiber Technology, Institute of Coal Chemistry, Chinese Academy of Sciences, 27 Taoyuan South Road, Taiyuan 030001, P.R. China

The self-stiffening under external dynamic strain has been observed for some artificial materials, especially for nanocomposites. The microstructures of the nanocomposites could be rearranged during external mechanical stimulations. The investigations of the self-stiffening phenomenon would deepen our understanding on the interactions between nanomaterials and polymer matrix as well as benefit the development of adaptive structural materials. However, few systematic studies have been done on their structural evolutions and the effect of the types of nanomaterials is unclear. In this study, we used a common semi-crystalline polymer, polyacrylonitrile (PAN), and various types of carbon nanomaterials including C60, carbon nanotube (CNT) and graphene oxide (GO). A periodic external strain at small amplitude of 0.2 % was applied on the prepared nanocomposite films. It was observed that PAN/CNT exhibited significant self-stiffening behavior, while PAN/GO showed no response to external dynamic strain. Systematic characterizations were performed to determine the structural evolutions of PAN/CNT film during dynamic strain testing, and it was found that the external dynamic strain not only induced crystallization of PAN in the interphase regions, but also aligned CNT along the straining direction. Also, the crystallization of PAN exhibited angular dependence on the strain direction. The dynamic strain provides an unique processing method to further develop the interphase structures of PAN/CNT nanocomposites to improve their performances even after the material has been shaped into film or fiber forms.

61

Effect of Ball-Milling On Supercapacitive Performance Of Expanded Graphene

Dong, Y1, Zhang, S2, Chen, X1, Zhou, J1, Ma Z.1, Jia D2, Song, H1*

[email protected]

1 State Key Laboratory of Chemical Resource Engineering, Beijing Key Laboratory of Electrochemical Process and Technology for Materials, Beijing University of Chemical

Technology, Beijing 100029, P. R. China *[email protected] 2 Xinjiang University, Urumqi, P. R. China

Supercapacitors have attracted huge attention due to their high power density, long life span, low maintenance cost. However, most researches are focused on their gravimetric performance and overlook the volumetric properties, which is a more valuable index in particle application. To overcome this problem, we prepared expanded graphite (EG) by rapid thermal expansion of graphite oxide. The EG samples were characterized before and after ball milling for several hours (denoted as EG-x, “x” represented the time of ball milling) to access their electrochemical characteristics as carbon electrodes for supercapacitors. The specific surface areas decreased drastically after ball milling. However, the capacitance of EG-x were similar to or even slightly higher than that before ball milling. Oxygen content was largely increased and much more defects and edge sites were formed by ball milling, which would contributed to the increase of the capacitance. Especially, the density of electrode materials increased to approximately 3400% of their original value after ball milling. The specific capacitance of EG-24 reached 135 F/cm3 (195 F/g) at 0.2 A/g in symmetrical two electrode capacitance, which is among the highest value in recent reports. Our work could help for advancing the design of graphene based supercapacitor electrodes.

62

Effect of Solvent Chemisorption on Wettability and Self-Assembly of Graphene

Md J Nine, Shervin Kabiri, Tran Thanh Tung, Dusan Losic Presenting author’s e-mail: [email protected]

School of Chemical Engineering, The University of Adelaide, Adelaide, SA 5005, Australia

Wettability of graphene derivatives becomes an important parameter for many applications that involves microfluidics, drug delivery, tissue engineering, surface coating, water harvesting and self-cleaning.[1-5] Herein, we demonstrated an effect of chemisorption of characteristic functional groups for various solvents (water, acetone, ethanol, Dimethylformamide (DMF), Tetrahydrofuran (THF)) on wettability and self-assembly of mechanically exfoliated multilayered graphene after performing a two-step sonication and ball-milling in order to prepare a highly dispersed graphene solution. The findings provide a new insight to tune wettability of conductive graphene surface by choosing suitable solvents for selective application where wettability is an important factor. Wettability ranges from hydrophilic (47° WCA) to superhydrophobic (>150° WCA) based on the solvent used in ultra-sonication and mechanical ball-milling. It was also found that the evaporation induced self-assembly of graphene dispersed into different solvents affected by the density and natural evaporation rate of different solvents. Surface morphology of these coatings have been identified different on glass-slide which are principally affected by the evaporation induced self-assembly. The graphite (<45 µm, 99.9 % pure) was expanded following a micro-wave assisted method. The oxygen functional groups in 1st step of ultrasonication in water makes the material active for further chemisorption in ball milling.[7] The longer duration (≈24 h) of strong ultrasonication of expanded graphite at water/acetone mixture of 60:40 ratio makes them exfoliated to produce multilayered graphene. The further 2nd step sonication and ball-milling was performed subjected to individual solvent for another 2 hr at a concentration of 1mg/ml. It was investigated that acetone based sonication turns the graphene surface from hydrophobic (115° WCA) to superhydrophobic (164° WCA) in contrast to the hydrophilic conversion by water and ethanol. DMF and THF are found to increase the contact angle from 115° to ≈ 140°. References 1. Nine, M.J., et al., Graphene: a multipurpose material for protective coatings. Journal

of Materials Chemistry A, 2015. 3(24): p. 12580-12602.

2. Kim, G.-T., et al., Wetting-Transparent Graphene Films for Hydrophobic Water-Harvesting Surfaces. Advanced Materials, 2014. 26(30): p. 5166-5172.

3. Preston, D.J., et al., Scalable Graphene Coatings for Enhanced Condensation Heat Transfer. Nano Letters, 2015. 15(5): p. 2902-2909.

4. Xuebin, T., Z. Zhixian, and C. Mark Ming-Cheng, Electrowetting on dielectric experiments using graphene. Nanotechnology, 2012. 23(37): p. 375501.

5. Nine, M.J., et al., Robust Superhydrophobic Graphene-Based Composite Coatings with Self-Cleaning and Corrosion Barrier Properties. ACS Applied Materials & Interfaces, 2015. 7(51): p. 28482-28493.

6. Notley, S.M., Highly Concentrated Aqueous Suspensions of Graphene through Ultrasonic Exfoliation with Continuous Surfactant Addition. Langmuir, 2012. 28(40): p. 14110-14113.

63

Efficient Graphitization Of LPI-CNFS Using Microwaves

Kamatari, S, Iwamura, S, Ogino, I, Mukai, SR

[email protected]

Hokkaido University, Sapporo, Japan

Previously we showed that extremely long carbon nanofibers (CNFs) can be synthesized at high carbon yields using the Liquid Pulse Injection (LPI) technique, a modified version of the floating catalyst technique. CNFs with lengths over 500 µm can be continuously produced at carbon yields close to 90%. Such LPI-CNFs possess superior properties at the as-grown state, but their properties can be significantly improved through graphitization. Graphitization processes are usually energy consuming and inefficient as temperatures over 2500 C are usually required, but we found that LPI-CNFs can be easily graphitized through simple microwave irradiation. As graphitization hardly occurred when commercially available CNFs were treated in a similar way, we assumed that the properties unique to LPI-CNFs led to efficient graphitization. By investigating how the properties of LPI-CNFs affects their graphitization behavior, we concluded that two unique factors of LPI-CNFs leads to such efficient graphitization. One is their nanostructure. LPI-CNFs consists of curved graphene sheets like typical CNFs, but the degree of alignment of the sheets are fairly high even at the as-grown state, as they can be converted to close-to-perfect MWCNTs by heat treatment at temperatures lower than 2000 C. The other factor is the extremely low apparent density of as-grown LPI-CNFs due to their extremely long lengths. As this density affects the intensity of the electric field formed within the irradiated CNFs which governs the heating efficiency of the material, we believe that as-grown LPI-CNFs have a suitable apparent density for efficient heating by microwaves.

64

Electrochemical Capacitance of a Transition Metal Doped Mof Derived Carbon

Chakraborty Banerjee, P1, Lobo, D.E1, Shaibani, M1, Majumder, M1

[email protected]

1Nanoscale Science and Engineering Laboratory (NSEL), Department of Mechanical and Aerospace Engineering, Monash University, Clayton, VIC 3800, Australia

We illustrate a novel concept in tailoring the architecture of MOF-derived carbons by doping MOF crystals with transition metal ions prior to carbon structure growth via chemical vapor deposition (CVD). MOF-5 was isomorphously doped with various concentrations of Ni2+ during synthesis and was subsequently subjected to CVD to grow a labyrinth of carbon nanofibers (CNF) with high electrical conductivity and higher surface area than that of the parent MOF. TEM of the inner structure of the CNFs revealed a chevron arrangement with ~0.34 nm visible fringe spacing. The CNF diameters increased with increasing Ni concentration. This is attributed to the decreasing distance between Ni dopants with increasing Ni concentration, which may facilitate coalescence of the Ni catalyst during the heat treatment and thereby increase the diameter of the resultant CNF. However, Ni doping concentration greater than 30% led to large agglomerations of Ni particles which eventually ceased CNF growth. The electrical conductivity and the electrochemical double layer capacitance of the CNFs also increased with increasing Ni concentrations. The highest electrochemical double layer capacitance and the lowest resistance was observed at a Ni doping concentration of 30%. An alkaline electrolyte was used to engage the Ni particles inside the CNFs to participate in a reversible redox reaction shuttling between Ni and Ni(OH)2, which resulted in a specific capacitance as high as 349 F/g. The possibility of doping transition metals into a wide variety of MOF structures can provide a new method to synthesize novel carbon structures with high energy storage capabilities.

65

Electronic-mechanical-magnetic coupling in 2D materials

Kou, L.


School of Chemistry, Physics and Mechanical Engineering Faculty, Queensland University of Technology, Garden Point Campus, QLD 4001, Brisbane, Australia

The discovery and exploration of graphene has stimulated intensive research in recent years, leading to the identification and study of a wide range of two-dimensional (2D) materials that exhibit a rich variety of novel structural, electronic, catalytic, and mechanical properties. We have shown that the magnetic properties in defect graphene1 and transition metal dichalcogenides2 are tunable with strain deformation. More interesting, we report findings of an extraordinary combination of unusual mechanical and electronic properties in hydrogenated borophene, known as borophane3, from first-principles calculations. This novel 2D material has been shown to exhibit robust Dirac transport physics4. Our study unveils that borophane is auxetic with a surprising negative Poisson’s ratio stemming from its unique puckered triangle hinge structure and the associated hinge dihedral angle variation under a tensile strain in the armchair direction. Our results also identify borophane to be ferroelastic with a stress-driven 90-degree lattice rotation in the boron layer, accompanied by a remarkable orientation switch of the anisotropic Dirac transport channels. References 1. L. Kou, C. Tang, W. Guo and C. Chen, ACS Nano 5 (2), 1012-1017 (2011). 2. L. Kou, C. Tang, Y. Zhang, T. Heine, C. Chen and T. Frauenheim, The Journal of Physical Chemistry Letters 3 (20), 2934-2941 (2012). 3. L.-C. Xu, A. Du and L. Kou, Physical Chemistry Chemical Physics 18 (39), 27284-27289 (2016). 4. L. Kou, Y. Ma, C. Tang, Z. Sun, A. Du and C. Chen, Nano Letters 16 (12), 7910-7914 (2016).

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66

Electrostatic-spraying an ultrathin, multifunctional coating onto a cathode for lithium-sulfur battery

Niu, S Z 1,2, Lv, W2, Kang, F Y1,2* and Yang, Q H 1,2,3*


1Tsinghua-Berkeley Shenzhen Institute (TBSI), Tsinghua University, Shenzhen 518055,

China 2Engineering Laboratory for Functionalized Carbon Materials and Shenzhen Key

Laboratory for Graphene-based Materials, Graduate School at Shenzhen, Tsinghua University, Shenzhen 518055, China

3School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072, China

For lithium-sulfur (Li-S) battery, the shuttle effect of polysulfides leads to an irreversible loss of sulfur and low Coulombic efficiency, hindering real applications of the Li-S batteries. In this work, we prepare a novel multifunctional polysulfide blocking layer (MPBL) directly coating on the cathode by employing a simple, one-step electrostatic spray deposition (ESD) technique. The ESD process is well manipulated for producing an ultrathin and composite coating and scalable for mass production. More promisingly, MPBL represents an ideally designed barrier layer and superior to the previously reported secondary barrier layers due to the following merits integrated in one thin layer. The MPBL is thin enough (~100 nm) to guarantee fast ion diffusion, ensuring the high rate capability, and slightly add the volume and weight of the device. Such a MPBL, with good conductivity derived from a combination of high conductivity carbon black and a conductive polymer, acts as the upper current collector to make the captured polysulfides reusable, and thus improve the utilization of active materials, which is important for real applications of Li-S batteries. As a result, the MPBL-coated cathode in this study exhibits good long cyclic stability with only 0.042 % capacity decay per cycle at 1 C for 1000 cycles. Even at a high rate of 3 C, it still delivers a capacity of 615 mAh g-1, exhibiting excellent rate performance. This study not only provides a simple approach to design high performance cathode for Li-S batteries, but also demonstrates a promising electrode protection design for broad energy storage devices. Thus, we believe this work will be of high interests to a broad audience.

67

On the Elucidation of the Layer Transition in Adsorbed Argon on Graphitized Thermal Carbon Black

Zeng, Y1, Prasetyo, L1, Tan, S1, Nakai, K2, Horikawa, T3, Do, D. D1, Nicholson, D1

[email protected]

1 University of Queensland, Brisbane, Australia 2 MicrotracBEL. Corp., Japan

3 The University of Tokushima, Tokushima, Japan

Adsorption of argon on a graphitic surface is widely studied using a homogeneous model for graphite with an energetically homogeneous surface, with a solid-fluid potential calculated with the Steele 10-4-3 equation using the molecular parameters: = 0.34nm and /k = 28K and a carbon atom surface density of 38.2 nm-2. An implicit assumption in this model is that the graphene layers are equally spaced. However, this model fails to capture the following important features observed in the experimental adsorption isotherm and isosteric heat: (1) the density jump in the monolayer region, which is associated with the 2D-liquid to 2D-solid transition; (2) the spike at the monolayer density in the isosteric heat curve versus loading; (3) the shorter distance between the first graphene layer and the remaining graphite as measured by LEED and RHEED because of the anisotropy of the vdW forces acting on this layer (i.e. no graphene layer to straighten it out above the free surface); (4) the over-prediction of the simulated isotherm in the multilayer region. To describe correctly these experimental observation we proposed a new model for graphite accounting for (1) the corrugation of the potential energy. (2) the reduced collision diameter of carbon atoms (0.28nm) in the uppermost graphene layer, (3) the increase in the interaction energy well depth between carbon atoms of the uppermost layer, and (3) the closer spacing between the first layer and second layer than the underneath layers. Introducing these features into the modelling, gives an improved description of the adsorption isotherm and isosteric heat, especially in capturing the transition from 2D liquid to solid-like adsorbate and subsequently to incommensurate solid, and the variation of these properties with temperature which has not been previously reported in the literature. In particular, our new simulations show the way in which adsorbed molecules rearrange themselves during the layer transition.

68

Energetic Parameters of Toxic Metals Adsorption from Aqueous on Solids with Different Surface Chemistry

Rodríguez-Estupiñán, P 1. Moreno-Piraján, J.C. 1, Giraldo, L. 2,

Gómez Granados, F2.

Presenting author’s e-mail: [email protected], [email protected]

1 Departamento de Química, Universidad de Los Andes, Bogotá D.C., Colombia 2 Departamento de Química, Universidad Nacional de Colombia, Bogotá D.C., Colombia

The importance of surface chemistry on the adsorption of metal ions from aqueous solution is mainly due to specific interactions between surface groups and dissolved species in solution. The effect of surface chemistry on the adsorption capacity of porous materials can be studied by immersion calorimetry, to establish relationships between the enthalpies of liquid immersion in aqueous solutions, and the ability to remove heavy metals such as nickel, cadmium and cobalt on adsorbents with different chemical and textural properties. Immersion calorimetry allowed to characterize the energy parameters of interactions present in the adsorption process, it was found that: (i) the enthalpy of immersion in benzene varies linearly with the surface area, given the effects of diffusion restriction by the inclusion of surface groups with different treatments, obtaining values were between -19.9 to -125J/g1. The same trend is observed in mesoporous silica and OMC; values for immersion in benzene are lower for functionalized samples. (ii) Ion adsorption on the surface of the solid also produces a thermal effect which may be evaluated to obtain the total amount of heat generated in the process. The enthalpy of immersion in the solution of Co (II) shows that oxygenated surface groups produce an increase in the strength of adsorption of ions by establishing different adsorption mechanisms such as donor-acceptor interactions. The enthalpies of immersion in solutions of electrolytes increased with the concentration of the solutions, these were higher for SBA-15 systems than GAC and OMC systems, showing the affinity and selectivity of solids by the respective ions.

69

Engineering the Surface States of Carbon Dots for Tuning Their Properties and

Functionalities

Li, Q.; Wang, S.; Kim, T.H.; Eftekhari, E. Presenting author’s e-mail: [email protected]

Queensland Micro- and Nanotechnology Centre & Environmental Engineering, Griffith

University, Nathan Campus, QLD 4111

Carbon nanodots (C-dots) including graphene quantum dots have emerged as an exciting new material in recent years, owing to their bright photoluminescence, biocompatibility, low to nil toxicity, and low cost. C-dots have been regarded as a viable alternative to semiconductor-based quantum dots (QDs), attracting significant research attention on both fundamental and applied sciences. Different from QDs, the surface states on C-dots play more significant role on their optical properties. In this talk, we will demonstrate the influence of surface states on C-dots’ photoluminescence, as well as show their importance in imparting functionalities to C-dots for applications in sensing, lighting devices and biomedical research.

70

Evaluation of Edges for Carbon Materials

K, Matsumura, T, Kinumoto, T, Tsumura, M, Toyoda

[email protected]

Oita University, 700 Dannoharu, Oita 870-1192, Japan

Controlling and evaluating the edges of carbon materials is important for their chemical

applications. The edges are chemically active and comprise various functional groups. However, accurate evaluation techniques for the edges have not yet been established. Accordingly, they are attempted to accurately quantify the total number of the edges, the number of the edges with oxygen bonded to functional groups, and the number of edges comprising other functional groups. Water is typically released from carbon materials by heating under an oxygen atmosphere. The amount of hydrogen released in the form of H2O indicates the total amount of hydrogen atoms directly bonded to the edges and the number of hydrogen atoms containing functional groups. Moreover, the number of functional groups not containing hydrogen is determined by TPD (Temperature Programed Desorption) measurements. The total number of edges can be determined from the total number of hydrogen atoms directly bonded to the edges, the number of hydrogen atoms containing functional groups, and the number of functional groups not containing hydrogen. Samples were made to undergo electrochemical oxidation in a HNO3 solution and exfoliation under an air atmosphere. A large number of edges were shown to be present with a high ration of functional groups. Herein, we evaluated the effect of the difference in time by oxidation treatment using H2SO4 on the formation of edges and functional groups of exfoliated carbon fibers and activated carbon through elimination of functional groups.

71

Fabrication and anti-ablation performance of W/Cu composite coatings by SAPS

L. Guo, J. Peng


State Key Laboratory of Solidification Processing, Carbon/Carbon Composites Research Center, Northwestern Polytechnical University, Xi'an, China

W/Cu composite coatings were prepared by supersonic atmosphere plasma spraying (SAPS) on SiC coated C/C composites substrate. The influence of spraying power was studied and result indicated that 45 kW is suitable to prepare W/Cu coating. The micro-hardness of W/Cu coating decreased with the increase of Cu content, and the bonding strength between W/Cu coatings and SiC coated C/C composites exceed 20 MPa. The anti-ablation properties of W/Cu coatings with different Cu content were studied under oxyacetylene torch and W12Cu (wt. 12% Cu) coating shows excellent anti-ablation performance. The linear ablation rate of W12Cu coating decreased by 63% under heat flux of 2.4 MW/m2, 87% under heat flux of 4.2 MW/m2 compared with pure W coating. During oxyacetylene ablation, the molten Cu film protect coating from oxidization, and continuously sweating and cooling effect of Cu phase make the surface temperature of W/Cu coating decrease by 300 at most, which is vital to good ablation resistance property of W/Cu coating.

72

Fabrication and Microwave Absorbing Properties of Hollow Graphene Spheres

Zhao, D L, Ding, Z W, Meng, S


State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing, China

Microwave absorbing materials have attracted more and more interest because of the facts that they can absorb energy from microwave and that they can be widely used in the stealth technology of aircrafts, television image interference of high-rise buildings, and microwave dark-room protection, etc. The manufacture of microwave absorbing materials involves the use of compounds capable of generating dielectric and/or magnetic losses when impinged by an electromagnetic wave. Extensive study has been carried out to develop microwave absorbing materials with high efficiency and new absorption materials. In our present work, microwave absorption, complex permittivity and permeability of the hollow graphene spheres have been investigated within the frequency range of 0.5-18 GHz, and the possible microwave absorbing mechanisms were discussed. The hollow graphene oxide spheres have been successfully fabricated from graphene oxide nanosheets utilizing a water-in-oil emulsion technique, which were prepared from natural flake graphite by oxidation and ultrasonic treatment. The hollow graphene oxide spheres were reduced to hollow graphene spheres at 500 ºC for 3 h under an atmosphere of Ar(95%)/H2(5%). Compared with the performances of graphene sheets, not only the matching frequencies of the prepared hollow graphene spheres have been shifted to higher values, but also the microwave absorbing frequency bands have been expanded, which thanks to the hollow structure, thin and porous shells consisting of graphene sheets.

73

Fabrication of hierarchical porous graphene microspheres and their adsorption

properties

Gong QM1, Sakamiya M1, Bai JF1, Liu X2, Huang YL1, Zhao M1, Zhuang DM1, Liang J1


1 Tsinghua University, Beijing, P.R. China 2 Beijing Institute of Technology, Beijing, P. R. China

Graphene has aroused great enthusiasm in scientific community in recent years for its excellent mechanical, thermal and electrical properties. Actually, all the aforementioned properties are quite sensitive to the perfectness of its in-plane crystal structure and size. In contrast, some defects in the graphitic structure would be beneficial to improve its adsorption properties for these active sites could be easily functionalized with suitable groups aiming at the adsorbates. While obviously, the as-prepared powdery graphene could not be utilized directly as adsorbents for the inconvenience of recycling and possible secondary pollution. Thus in this paper, a new strategy of freeze casting was proposed to fabricate graphene or graphene oxide based microspheres with hierarchical porous structure. BET analyses and SEM observations indicated that besides highly developed mesopores, a radial porous structure was also created by this unique synthesis process. By adjusting the freezing agents, the pore structure could be modified conveniently. Nano CT analyses indicated that the pore structure was exactly the mirror image of the crystalline of the solvent in the suspension. Adsorption experiments demonstrated that the adsorption capacity of VB12 for the composite graphene/chitosan microspheres could reach 111.3mg/g. Moreover, the porous microsphere could also act as efficient adsorbents of HBV(hepatitis B virus).The remarkable adsorption properties could be attributed both to the micrometer-sized radial pores which could act as direct channels for adsorbates diffusing and to the highly developed mesopores which might act as adsorbing sites.

74

Facile Close-packed Monodisperse Carbon Nanospheres for High S-loading Li-S Batteries

Hu, C1 and Biggs, MJ1,2

[email protected]

1 School of Science, Loughborough University, Loughborough, UK 2 School of Chemical Engineering, The University of Adelaide, Australia, 5005.

The high specific capacity (1672 mAh/g) and low cost of sulfur means lithium-sulfur (Li-S) batteries are amongst the most promising candidates for supplanting the now near-ubiquitous Li-ion batteries. Per unit volume, Li-S batteries are expected to deliver at least the same energy as Li-ion batteries whilst being substantially lighter and cheaper. One key challenge to delivering on this promise is to increase the areal sulfur loading whilst retaining high sulfur utilization and cell efficiency. In this contribution, we present the study of a novel microporous carbon-based Li-S cathode synthesised from a template-free phenol resin precursor. The carbon is composed of highly monodispersed 300 nm nitrogen-doped carbon nano-spheres with microporosity of 1.2 cm3/g and N2 BET specific surface area of 2900 m2/g. The spheres are observed to form interconnected close-packed clusters over a few µm. The abundant micropores with N-doped surfaces help ensure high cell stability over 100s of charge-discharge cycles. The particle packing enables a uniform thick coating of sulphur to be achieved using a conventional slurry approach. The free space between the spheres provides good ion diffusion channels. A 5mg/cm2 S cathode delivers an initial sulfur specific capacity (Cs) of 1080 mAh·g-1 at 0.5C. Over 500 charge-discharge cycles at 0.5C, the average Cs fading per cycle is just 0.1%. These results combined with the fact that the carbon was derived using standard methods makes the material competitive for industrial scale-up.

75

Fe/N/P tridoped biomass derived carbon electrocatalyst for highly efficient ORR

Yahao L1, De C1


1 Department of Chemical Engineering, Norwegian University of Science and Technology, Sem Sælands vei 4, 7491 Trondheim, Norway

Within all electric energy storage devices, metal-air battery is attractive for its high energy density, high capacity and low fabrication cost. To fabricate a high quality metal-air battery, an efficient catalyst for oxygen reduction reaction (ORR) is essential. Platinum (Pt) base catalysts, including Pt alloy, are by far the most efficient among all catalysts. However, as one of the noble metal, the lack of abundance of Pt lead to the high cost, which hinders its commercial applications. Recent studies revealed that nitrogen doped carbon nanomaterials possess impressive ORR activities, and co-doping phosphorus into the materials can further enhance the ORR activity due to the modulation of electronic properties and surface polarities. Meanwhile, carbon supported iron-nitrogen complexes Fe-Nx were also believed to be an effective active site for ORR. Both strategies can lead to excellent electrocatalysts, and combining them together may result even better catalysts. Here we present a novel Fe/N/P tri-doped carbon catalyst derived from lignocellulose (FeNPL), with superior activities of onset and half-wave potential of 1.050 V and 0.874 V (vs. RHE) that even surpass the performance of 30 % Pt/C catalyst. It presents a cost alternative production of the co-doped carbon materials by one-step pyrolysis of woody biomass. While utilized as air-electrode in Zn-air battery, gorgeous performances of open-circuit potential of 1.48 V, an energy density of 771 Wh/kgZn and a peak power density of 100 mW/cm2 were also achieved.

76

Features Soot and Nanomaterials Formation in Coaxial Flame

Lesbayev B.T.1,3, Prikhodko N.G.1,2, Nazhipkyzy M.1,3, Smagulova G.T.1,3, Isanbekova A.T.1,3, Turganbay A.1,3, Temirgaliyeva T.S. 1,3, Janzakova K.M.1,3, Temirgaliyeva A.3,

Mansurov Z.A.1,3

[email protected]

1 Institute of Combustion Problems, Almaty, Kazakhstan 2 Almaty University of Energetics and Communications, Almaty, Kazakhstan

3 Al-Farabi Kazakh National University, Almaty, Kazakhstan

Soot of various modification is widespread material to create composites. At the same time structure and properties of soot particles depends on the method of synthesis, also of the starting fuel components and technological synthesis conditions. One of the promising methods of producing carbon black is process of synthesis at hydrocarbons combustion. Currently, research related to nucleation and growth of the carbon product in the flame indicate that their formation does not occur instantaneously, but through a sequence of elementary reactions between short-lived intermediate particles (radicals, ions, etc.). From the above, the composition, structure and properties of the final combustion products formed in the flame will depend on the of concentrational density and of the combination of the nature of the intermediate particles. These parameters are specific to a particular type of fuel, depending on its chemical composition. We propose to organize the simultaneous coaxial burning different fuels, when the initial flames burning phase for different kinds of fuels takes place on an individual basis, with the further association of flames at a certain height from the burner to form separate a combined of the reaction zone. This condition is allows to the predetermine the structure of soot particles and other nano-materials in the process of their formation, by changes in the combined reaction zone coaxial flame concentrational density and composition of intermediate species by the selection of fuels. In the present work we investigated in the coaxial flame of the soot formation process with predetermined properties and carbon nanomaterials.

77

Femtosecond laser exfoliation of graphite fluorides

Batisse, N1, Herraiz, M1, Peyroux, J1, Dubois, M1,


1 Institut de Chimie de Clermont-Ferrand (ICCF), Université Clermont Auvergne, UMR CNRS 6296, 63177 Aubiere, Cedex, France

In order to produce graphene materials, laser irradiation have been largely studied for the reduction of graphene oxide. Beside these precursor, graphite fluoride could also be of a particular interest for the synthesis of graphene, in order to facilitate exfoliation and to reach a better control of the surface chemistry. Here we investigate the exfoliation of graphite fluoride by laser irradiation with ultra-short femtosecond pulses. On one hand, in the case of graphite fluoride synthesised by direct fluorination of highly ordered pyrolytic graphite in fluorine gas atmosphere, an anisotropic behaviour is observed based on the orientation of the flakes under the laser beam. Normal incidence leads to ablation of the material whereas tangential incidence allows a fast exfoliation of the particle. Even with a focused beam of several micrometres and short irradiation times of hundreds of milliseconds, exfoliation propagates on large distances (several millimetres) due to gas generation produced by defluorination and energy transfers in the material over short timescales. The atmosphere used during irradiation (either air or neutral gases) directly impacts this phenomenon, and as a consequence the graphene materials produced. On the other hand, micrometres sized graphite fluoride flakes demonstrate no orientation effects. Particularly, laser induced forward transfer (LIFT) mode is employed to displace the exfoliated particles out of the laser focus to avoid their ablation, and allows in addition a spatially selective deposition of the graphene materials.

78

Fe-N-doped carbon catalysts prepared by PECVD/sputtering system for fuel cells

Hotozuka, K1, Yoshie, R2, Taniguchi, M2, Murata, H2, Tachibana, M2

[email protected]

1 IHI Corporation, Yokohama, Japan 2 Yokohama City University, Yokohama, Japan

Carbon-based materials containing transition metal-nitrogen (M-N) coordination structures have attracted much attention as promising non-Pt catalysts in polymer electrolyte fuel cell (PEFC). The high temperature treatment leads to the formation of stable graphitic carbon structure whereas it gives rise to the breakdown of the M-N coordination bonds which are favourable to oxygen reduction reaction (ORR). Therefore, the low temperature synthesis is desirable for the synthesis of carbon-based materials containing M-N coordination structure. The plasma-enhanced chemical vapor deposition (PECVD), which has been widely used for the synthesis of vertical aligned nanocarbon materials such as carbon nanotubes and carbon nanowalls is of interest for the low temperature synthesis of carbon-based materials including M-N coordination structures. In this paper, we report a low temperature hybrid PECVD/sputtering system to synthesize Fe-N-doped carbon catalysts for ORR. This hybrid system combines dc-PECVD effective for the synthesis of nanocarbons with sputtering technique for the doping of metals such as Fe where the amount of the doping can be independently controlled during synthesizing nanocarbons. By using this system, the Fe-N-doped carbon catalysts are directly synthesized on carbon papers composed of an open mesh of carbon fibers, which have been widely used as a gas diffusion layer in PEFC. The synthesized materials with carbon fibers exhibit high ORR activity. It is clarified that the high ORR activity is attributed to Fe-N coordination structures which are stably formed in the synthesized ones.

79

Filling Mechanisms, Composition, Structure, And Properties of Halide-Filled DWCNTs

Nie, C.1,2, Zubair, A.3, Tristant, D.1,4, Monthioux, M.1


1CEMES, UPR-8011 CNRS, Université Toulouse III, Toulouse, France 2CIRIMAT, UMR-5085 CNRS, Université Toulouse III, Toulouse, France

3Dpt of Electrical and Computer Engineering, Rice University, Houston, Texas, USA 4LPCNO, UMR-5215 CNRS, INSA, Université Toulouse III, Toulouse, France

Various halides including iodine were introduced into double-wall carbon nanotubes (DWCNTs) by the molten or the gas phase methods. H2 reduction was eventually performed for obtaining encapsulated metal nanowires. A variety of encapsulated 1D nanocrystals were obtained, as investigated by high-resolution transmission electron microscopy (HRTEM) using various modes. Local chemical compositions and structure were revealed by electron energy loss spectroscopy (EELS), image calculation, and modelling. A clear understanding of the parameters driving the filling rates was obtained, while related anomalies were explained. Then the work focused on iodine-filled DWCNTs, as encapsulated iodine exhibited a variety of atomic structuration inside and outside the nanotubes which was found to be driven by the available space being filled. Relying on DFT calculations supported by atomically-resolved TEM, we demonstrated that two I2 in contact with or inside CNTs could interact to form I3- and I- along as well as I42- with generating a dramatic charge transfer to the nanotube. This was further supported by Raman spectroscopy, which can be used to determine the doping level more easily when the iodine species are in contact with the outer nanotube. In this case, considering polyiodide and monoiodide was necessary to explain the observed large doping level. The doping effect was large enough to account for the conductivity level of iodine-filled DWCNT-based fibres. Other co-authors: Galibert A.-M., Soula B., Flahaut E., Datas L., Gerber I.C., Puech P., Sloan J., Tsentalovich D.E., Headrick R.J., Pasquali M., Kono J.

80

Flexible Fiber-type Transistors from Graphene Hybrid Fibers

Jea Uk Lee


Korea Research Institute of Chemical Technology (KRICT),Daejeon, South Korea

Wearable electronic materials, such as electronic textiles, have recently attracted great interest because they present exciting possibilities for interfacing computers/ processors, sensors, displays, and energy devices with the human body. To truly realize wearable smart electronics, every component in the electronic units should be flexible, lightweight, and directly integrated into three-dimensional textile structures. In this work, we report the fabrication of flexible fiber-type field-effect transistors using graphene/metal nanoparticle hybrid fibers as highly conductive and flexible electrodes. The graphene hybrid fibers were prepared by the wet-spinning of graphene oxide and hybridization with Ag nanoparticles. The fiber-type transistors were constructed by continuously embedding the graphene/Ag hybrid fiber electrodes and transferring the semiconductor/ion-gel dielectric layers onto conventional polyurethane monofilaments, and exhibited excellent flexibility (highly bendable and even stretchable) and high electrical performance.

81

Fluorinated Carbide-Derived Carbon for Gas Sensor and Energy Storage

Guerin, K1, Batisse, N1, Dubois, M1, Ghimbeu, C, M2, Bhatia, S, M3, Brunet, J4, Simon, P5

[email protected]

1 Université Clermont Auvergne, CNRS, SIGMA Clermont, Institut de Chimie de Clermont-Ferrand, F-63000 Clermont–Ferrand, France.

2 Institut de Science des Matériaux de Mulhouse, CNRS UMR 7361-UHA, 15 rue Jean Starcky, 68057 Mulhouse, France

3 School of Chemical Engineering, The University of Queensland, Brisbane, QLD 4072, Australia

4 Université Clermont Auvergne, CNRS, Institut Pascal, F-63000 Clermont–Ferrand, France.

5 Centre Interuniversitaire de Recherche et d’Ingénierie des Matériaux(CIRIMAT), UMR CNRS 5085, Universite Paul Sabatier, 118 route de Narbonne, 31062 Toulouse, France

Since a decade, a new way to produce nanoporous carbons consists in chlorination of carbide in order to etch metallic atoms and to leave the carbon matrix. Gaseous molecular chlorine reacts with metallic atoms at high temperature (600 – 900°C) to form most of the time a gaseous chloride which is easily removed and carbon called carbide derived carbon (CDC). The unique nanoporous structure of CDC together with the narrow pore size distribution and possibility to tune the pore size distribution has noticeably forced the development of applications requiring the nanoporous materials such as adsorption processes, hydrogen storage, sensing, supercapacitors… We investigate the effect of fluorine-functionalisation of nanoporous carbide-derived carbon, on its structural as well as adsorption, sensing and electrochemical properties. Different fluorination ways can be conducted on CDC such as static fluorination with pure fluorine gas, dynamic fluorination with pure fluorine gas and controlled fluorination by atomic fluorine formed in situ by thermal decomposition of XeF2. All the fluorinated CDC have been characterized by thermo programmed desorption, X-ray diffraction, solid state nuclear magnetic resonance, infra-red and Raman spectroscopy in order to determine the nature of the C-F bonding. The fluorination mechanism differs owing to the 3 fluorination ways and has a direct consequence on the porous distribution. As a consequence the performances of the fluorinated CDC can be adjusted to each specific application.

82

Fluorinated nanodiamonds as unique neutron reflector

Nesvizhevsky, V1, Jentschel ,M1, Koester, U1, Dubois M2, Batisse N2, Frezet L2, Bosak A3, Gines L4, Williams O4


1Institut Max von Laue – Paul Langevin, 71 avenue des Martyrs, F-38042, Grenoble, France


3European Synchrotron Radiation Facility, 71 avenue des Martyrs, F-38042, Grenoble, France

4School of Physics and Astronomy, Cardiff University, Queen’s Building, The Parade, Cardiff, CF24 3AA, UK

.

We propose a new type of albedo-reflectors for slow neutrons (SNs) based on powders of designed fluorinated nanodiamonds. The reflectivity of commercially available detonation nanodiamonds (NDs) materials is measured to be much higher than that for any alternative reflector. However, neutron losses which occur in raw NDs powders are largely dominated by hydrogenated impurities and sp2 carbons shell onto diamond core. We overcome those principal difficulties using fluorinated nanodiamonds. We produced a sample of such powder and performed a series of neutron and X-ray measurements with this powder in order to quantify its parameters. The total removal of H atoms and sp2 shell onto diamond core is evidenced by prompt-γ analysis, multinuclear solid state NMR, Raman and IR spectroscopies. Based on these results, we simulated diffusion of SNs in the powder and showed that it provides unprecedented albedo, bridging so-called the reflectivity gap between SNs and thermal neutrons. Carbon reflectors provide excellent albedo also for thermal neutrons due to the Bragg scattering, and for faster neutrons due to the scattering on C nuclei, thus resulting in composite materials for moderation and reflection of neutrons in the complete energy range from neutron production down to neutron applications. The high reflectivity allows improving dramatically the performance of neutron sources, the efficiency of neutron delivery, and thus fluxes at neutron instruments; it will allow designing a new generation of neutron sources and experiments.

83

Formation and catalytic activity for oxygen-reduction-reaction of fullerene-soot-derived onion-like carbons

Takigami, M1, Maie, T1, Nariduka, K1, Takasu, K1, Kannari, N1, Ishii, T1., Ozaki, J1


1Gunma University, Kiryu, Japan

Onion-like carbons (OLCs) can be produced by several methods; intense electron irradiation of carbon soot, conversion of nanodiamonds to OLCs by heat treatment above 1700 , arc discharge of graphite and combustion of naphthalene. Fullerene soot (FS) is a by-product carbon material of fullerene production. In this study, we report the formation of onion-like carbon (OLC) from FS by oxidative heat-treatment. The FS used in the present did not explicitly show the presence of OLCs under transmission microscope; however, the heat-treatment at 600 in a stream (O2/N2=6/94) resulted in the formation of OLCs with corrugated graphitic layers. A temperature programmed XRD (TP-XRD) study was conducted to understand the details of the OLC formation from FS. The XRD profile of FS was broad ranging from 2 = 10 to 30 °, indicating the material substantially consisted of multiple components. The diffraction at 2 = 24 ° was developed with the heat-treatment temperature at the expense of the diffraction 2 = 14 °. This can be interpreted as the oxidative heat-treatment selectively removed the reactive amorphous carbon to expose the OLC structure embedded in it. This idea was confirmed by the no-formation of OLC structure by the heat-treatment in a nitrogen stream at the same temperature. The electrocatalytic activity of the oxidative heat-treated FS for oxygen reduction reaction improved with the heat-treatment time at 600 . These results suggested that the corrugated graphitic layers on the OLC should be responsible for the ORR activity.

84

Framework-mediated synthesis of Microporous Carbon Onion from a Porous Aromatic Framework

Shaibani, M1,2, Smith, S. J. D.2, Chakraborty Banerjee, P1, Hollenkamp, A. F.2, Hill, M. R.2,

Majumder, M.1


1 Monash University, Melbourne, Australia 2 CSIRO, Melbourne, Australia

Graphitic carbon, with its benchmark electrochemistry, densifies during formation, diminishing the effective surface area for charge storage. Consequently, synthetic strategies delivering narrowly distributed micropores are key. Here, we present a pathway to graphitic carbon with narrow, regular and connected pores from the precursor structure. The uniform, 3-D connected porosity and sp3 carbon of the porous aromatic framework PAF-1 maintained their diamondoid topology to a higher calcination temperature, preventing pore collapse during graphitization. The resulting structure, Microporous Onion-like Carbon (MOLC), had a surface area of 1084 m2g-1, 80 % derived from micropores, templated from the PAF-1 biphenyl units. MOLC delivered remarkable supercapacitance, 211 F g-1 at 5 mV s-1, and unprecedented 52 % capacitance retention at ultrafast 2000 mV s-1. We conclude that carbonaceous precursors like PAF-1 with regular pores connected by sp3 carbon delivers both microporosity and stability at temperature, and in turn a new carbon structure, with unprecedented supercapacitance.

85

Graphene Coatings as Barrier Layers to Prevent the Water-Induced Corrosion of Silicate Glass

Wang, B1, Cunning, BV1, Park, S-Y12, Huang, M12, Kim J-Y12, Ruoff, RS123


1 Center for Multidimensional Carbon Materials (CMCM), Institute for Basic Science (IBS), Ulsan, 44919, Republic of Korea

2 School of Materials Science and Engineering, Ulsan National Institute of Science and Technology (UNIST), Ulsan, 44919, Republic of Korea

3 Department of Chemistry, Ulsan National Institute of Science and Technology (UNIST), Ulsan, 44919, Republic of Korea

Corrosion-protective coatings for silicate glass based on the transfer of one or two layers of graphene grown on copper by chemical vapor deposition are demonstrated [1]. The effectiveness of graphene layers to act as a glass corrosion inhibitor was evaluated by water immersion testing. After 120 days of immersion in water, bare glass samples had a significant increase in surface roughness and defects, which resulted in a marked reduction in fracture strength. In contrast, the single- and double-layer graphene-coated glasses experienced negligible changes in both fracture strength and surface roughness. The study of the anticorrosion mechanism revealed that water could penetrate into graphene-coated glass, albeit at a reduced rate. Subsequent corrosion was prevented as graphene was shown to block sodium ions leeching from glass into the water. This work was supported by IBS-R019- D1. [1] Bin Wang, Benjamin V. Cunning, Sun-Young Park, Ming Huang, Ju-Young Kim, and Rodney S. Ruoff, ACS Nano, 2016, pp 9794–9800.

86

Graphene Doped Based Electrocatalyst For Fuel Cell Applications

Lemes, G.1, Luque-Centeno, J. M.1, Martínez-Huerta, M.V.2, Pastor, E.3, Lázaro, M.J.1.


1Instituto de Carboquímica. CSIC, Zaragoza, Spain. 2Instituto de Catálisis y Petroquímica. CSIC, Madrid, Spain.

3Instituto de Nanomateriales y Nanotecnología, Universidad de La Laguna, La Laguna, Spain.

Recently, graphene oxide (GO) and reduced graphene oxide (rGO) based materials have been proposed to replace noble metals (as Pt) in alkaline membrane fuel cells (AMFCs) because their high activity toward oxygen reduction reaction (ORR). Moreover, it is possible to model graphene properties through doping strategies with heteroatoms (N, P, S, B) which can modify the electronic structure. However, rGO doping procedures accept a limited amount of heteroatoms. On the other hand, carbon nitride (CN) has a similar structure to nitrogen doped reduced graphene oxide (NrGO) but a greater percentage of nitrogen. Therefore, NrGO-CN composites are the route to get a graphene based structure with nitrogen content as high as 35 %. The objective of this work is the synthesis of NrGO and NrGO-CN composites in order to evaluate their performance toward the ORR in alkaline media. GO has been synthesized from graphite by the modified Hummers method, whereas NrGO and NrGO-CN composites have been obtained by thermal and hydrothermal treatments of GO and urea mixture at different temperatures. Nitrogen composition of samples goes from 8 % to 35 %. These materials have been characterized using X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and elemental analysis. Catalytic activity for the ORR has been measured using a rotating disk electrode (RDE) in alkaline media. It was observed that the onset potential and the currents in the diffusion controlled region depend on the content of N, achieving the best results with NrGO-CN composite produced at 800ºC.

87

Graphene for Polymer Composites

Ma J


1University of South Australia, Adelaide, Australia

In comparison with metals and ceramics, polymers have been increasingly more used in industries over the past five decade owing to their relatively high specific strength and low manufacturing costs. However, most polymers are inherently limited by low stiffness and lack of functionality such as electrical conductivity. In spite of extensive studies conducted to utilize carbon nanotubes and silicate layers to address the limitations, the rise of graphene [1,2] now provides a more promising candidate due to its exceptionally high mechanical performance and electrical and thermal conductivities. My research team since 2008 has conducted extensive research of developing new graphene sheets [3–5] and using them for processing of epoxy [6,7], elastomers [8–10] and conducting polymers [11,12]. This presentation will introduce the graphene platelets and their polymer composites developed in my team. Reference:

1) K Geim, KS Novoselov, Nature Materials, 2007, 6, 183–191. 2) D Li, MB Müller, S Gilje, RB Kaner, GG Wallace, Nature nanotechnology, 2008, 3,

101–105. 3) I Zaman, HC Kuan, N Kawashima, A Michelmore, J Ma, et al. Nanoscale, 2012, 4,

4578–86. 4) I Zaman, HC Kuan, Q Meng, A Michelmore, J Ma, et al. Adv. Funct. Mater., 2012,

22, 2735–43. 5) G Shi, A Michelmore, J Jin, J Ma, et al. Journal of Materials Chemistry A, 2014, 2,

20382–92. 6) J Ma, Q Meng, A Michelmore, HC Kuan, et al. J. Mater. Chem. A, 2013, 1, 4255–64. 7) J Ma, Q Meng, I Zaman, HC Kuan, et al. Compos. Sci. Technol., 2014, 91, 82–90. 8) S Araby, I Zaman, Q Meng, J Ma, et al. Nanotechnology, 2013, 24, 165601. 9) S Araby, L Zhang, HC Kuan, J Ma, et al. Polymer, 2013, 54, 3663–70. 10) G Shi, Z Zhao, L Zhang, J Ma, et al. Adv. Funct. Mater., 2016, 26, 7614–25. 11) M Moussa, Z Zhao, MF EI-Kady, J Ma, et al. J. Mater. Chem. A, 2015, 3, 15668–74. 12) Z Zhao, M Moussa, G Shi, J Ma, et al. Compos. Sci. Technol., 2016, 127, 36–46.

88

Graphene Industry: Synthesis Determines the Future

Zhongfan Liu

Beijing Graphene Institute (BGI)

Center for Nanochemistry(CNC), Peking University, Beijing 100871, China

Graphene fever has passed over a decade since its first isolation in 2004 and a great number of applications have been demonstrated in laboratories and even at industrial scale. However, a huge gap still exists between the ideality and the reality. The ideal graphene material is composed of single crystalline hexagonal honeycomb lattice of sp2 hybridized carbon atoms while the experimentally available graphene is a polycrystalline film with lots of structural defects and unexpected noncarbon impurities. As a result, the observed properties of graphene are far from theoretical predictions. The key to bury this gap is the controlled synthesis towards perfect graphene. It is no doubt that the synthesis will determine the future of graphene material. On the other hand, it is also a crucial challenge to find out the killer applications of graphene, which would create a realistic graphene industry.

We are targeting to build the footstone of future graphene industry from the material synthesis point of view. We have made great efforts to grow high-quality graphene film on copper foil towards industrial level mass production. Currently we are able to grow cm sized single crystalline graphene film with high growth rates. For practical applications, we have succeeded in growing high quality graphene films on traditional glasses. The graphene endowed glass with extremely high thermal and electrical conductivities, leading to a new type of super graphene glasses. In a similar way, the graphene film has been deposited onto optical fibers under a high-temperature growth process, creating a graphene-decorated optical fiber. Various promising applications are demonstrated with these super graphene glasses and graphene-covered optical fibers.

89

Graphene Quantum Dots for Bio-imaging and Optical Sensing

Chen, P.

Email: [email protected]

School of Chemical & Biomedical Engineering, Nanyang Technological University (Singapore)

Due to some intrinsic limitations suffered by the current fluorophores (e.g., fluorescent proteins, organic dyes, and semiconductor quantum dots), seeking complementary or better fluorescent reporters is a constantly ongoing effort critical for the areas of bio-imaging, optical sensing, photovoltaics etc. Graphene quantum dots (GQDs or 0D graphene) are atomically-thin and nanometer-wide planar structures of pristine or modified graphitic carbon. They are emerging as a new class of fluorophores with unique combination of several key merits including widely tunable photoluminescence (PL) properties, excellent photostability, molecular size, biocompatibility，and good solubility. GQDs promise a wide range of novel applications in biomedicine, energy storage and conversion, catalysis, etc. In this presentation, we demonstrate the methods to synthesize GQDs and the applications of these GQDs for real-time molecular tracking in live cells, ultrasensitive fluorescence detection of biomolecules, and monitoring of dynamic cellular redox homeostasis.

90

Graphene-Based Adenosine Aptasensors: Elucidating Mechanisms at the Molecular-Scale

Hughes, Z.E.1 and Walsh, T.R.1


1 Institute for Frontier Materials, Deakin University, Geelong, VIC 3216,Australia

The combination of DNA aptamers with nanomaterials such as graphene can be utilised in biosensors able to detect nanomolar concentrations of target analytes in real time. However, to fully realize the potential of such biosensors, a deeper molecular-level understanding of the interfacial interactions is required. Experimental approaches can reveal the structure of DNA aptamers in aqueous solution, but this cannot be readily accomplished when the DNA is adsorbed on the electrode surface. Therefore, establishing clear connections between the structure of the adsorbed aptamer and its properties, under aqueous conditions, is challenging to obtain via experimental techniques alone. Molecular simulation is a complementary approach that can provide valuable details on the structural properties of DNA aptamers adsorb at device interfaces. Here we report results of extensive molecular dynamics simulations of an adenosine-sensing DNA aptamer in both the presence and the absence of the analyte, in the presence and absence of the aqueous graphene interface. Our results reveal that regardless of the presence of the analyte, the aptamer can non-covalently adsorb at the aqueous graphene interface, with both cases supporting substantial intra-aptamer interactions. Furthermore, we find that a greater number of nucleobases are adsorbed at the graphene interface in the presence of the analyte. This finding is consistent with recent single molecule force spectroscopy measurements that revealed a stronger interaction between the aptamer and a graphite interface in the presence of adenosine. Our work highlights the advantages of molecular simulation as a tool for understanding the structure of DNA aptamer-graphene biosensors.

91

Graphene-Based Materials for Flexible and Planar Micro-Supercapacitors

Wu Zhong-Shuai1, Zheng Shuanghao1, Wang Sen1, Qin Jieqiong1, Shi Xiaoyu1


1Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China

Micro-supercapacitors (MSCs) are important on-chip micro-power sources for miniaturised electronic devices. Using 2D atomically thin graphene, new designs for thin-film planar MSCs with outstanding performance have become possible, taking full advantage of the atomic layer thicknesses and flat morphology of graphene. In this talk, I will present our recent advances on the reasonable fabrication and construction of high-performance graphene-based MSCs. First, we demonstrate graphene-based in-plane MSCs through micropatterning of methane-plasma reduced graphene (MPG) films, delivering a power density of 495 W cm3 that is higher than electrolytic capacitors, and an energy density of 2.5 mWh cm3, and allowing for operations at ultrahigh rate up to 1000 V s1, three orders of magnitude higher than conventional supercapacitors. Second, we describe the development of large-area, highly uniform, ultrathin, nitrogen and boron co-doped graphene films for high-performance MSCs, providing an ultrahigh volumetric capacitance of 488 F cm3, and an ultrahigh operation scan rate of up to 2000 V s1. Third, we present a universal protocol for the construction of graphene compact films (graphene-based mesoporous polyaniline/polypyrrole, activated graphene, thiophene nanosheets) for high energy MSCs. For instance, graphene-conducting polymer films showed landmark areal capacitance of 368 mF cm-2, volumetric capacitance of 736 F cm3 for high-energy MSCs, and volumetric energy density of 46 mWh cm−3 that is the highest value reported to date. Therefore, these achieved MSCs have great promise as micropower sources for direct integration into various electronic circuits for future portable, wearable, and implantable microelectronics.

92

Graphene-Based Nanoionics

Li, Dan


Monash Centre for Atomically Thin Materials, Department of Materials Science and Engineering, Monash University, Melbourne, VIC 3800, Australia

Nanoionics is the study and application of properties, phenomena, and mechanisms of ion transport and storage in nanoscale systems. Despite being the key to a myriad of indispensable technologies in energy, water and biomedicine, our experimental understanding of confined ion transport at length scales below 10 nm, particularly below 2 nm, has so far been limited in terms of scale itself, but also of materials investigated. This talk will present how the layered graphene hydrogel membranes developed in my group in the past years could open up exciting opportunities for advancing the field of nanoionics and enable new nanoionic devices for energy storage and conversion, water purification and biomedical areas.

93

Graphite nanoplatelet/carbon nanofiber-based hybrid epoxy composites for thermal

interface applications

Raza MA1, Westwood A2, Stirling C3

Corresponding author email: [email protected]

1College of Engineering and Emerging Technologies, University of the Punjab, Lahore,

Pakistan 2School of Chemical and Process Engineering, University of Leeds, LS2 9JT, UK

3Morgan Advanced Materials, Swansea, SA6 8PP, UK (current address: Haydale Ltd., Ammanford, SA18 3BL, UK)

Thermal interface materials (TIMs) are important to the electronic packaging industry as they facilitate heat dissipation in microelectronics by overcoming thermal contact resistance between mating heat source / heat removing surfaces. Carbon nanomaterials such as graphene, carbon nanotubes (CNT), vapour grown carbon nanofibers (VGCNF) and graphite nanoplatelets (GNPs) have been extensively researched as nanofillers for TIMs. These nanofillers, when incorporated in polymer matrices, substantially improve thermal conductivities and mechanical properties of resulting composites. Synergies in composite properties have been reported upon mixing one dimensional (CNT or VGCNF) and two dimensional (GNPs or graphene) carbon nanofillers in a polymer matrix to produce hybrid composites.

This research reports a hybrid composite that incorporates GNPs and VGCNF, produced by dispersing these fillers in rubbery epoxy matrix by three roll milling. SEM analysis showed that VGCNF improved the dispersion of GNP in epoxy, compared to GNP/epoxy composites. However, the thermal conductivity of a composite produced with 20 wt.% loading (VGCNF:GNP, 1:1 by weight) was found to be 1.57 W/m.K which was half that of 20 wt.% GNP/epoxy (but 1.4x greater than 20 wt.% VGCNF/epoxy). Compressive strength and failure strain of the hybrid composite were higher than for non-hybrid composites containing 20 wt.% GNP or VGCNF. Thermal contact resistance measurements showed that GNP/VGCNF/epoxy hybrid composite offered lower thermal transport than 15 wt.% VGCNF/epoxy as TIM adhesive at thin bond lines despite the former’s higher thermal conductivity, but offered better thermal transport than 20 wt.% GNP/rubbery epoxy composite, suggesting that incorporation of VGCNF improves thermal contacts.

94

Graphitization of amorphous carbons: A comparative study of interatomic potentials

de Tomas, C1, Suarez-Martinez, I1, Marks, NA1

Presenting author’s e-mail: [email protected] 1 Curtin University, Perth, Australia

Over the past three decades atomistic simulations have made a significant contribution to the understanding of carbon materials. Many of these studies have only been possible through the development of interatomic potentials capable of describing the flexible hybridization states and anisotropic bonding present in carbon. Since the landmark Tersoff potential was developed in 1988, more than 40 interatomic potentials for carbon have been proposed. The challenge for the computational practitioner is to have confidence that the potential selected for a given simulation has sufficient transferability to be applied to the task at hand. In this work [1,2] we perform a comparative study of six common carbon interatomic potentials: Tersoff, REBO-II, ReaxFF, EDIP, LCBOP-I and COMB3. To ensure fair comparison, all the potentials are used as implemented in the molecular dynamics package LAMMPS. Using the liquid quenching method we generate amorphous carbons at different densities, and subsequently anneal at high temperature. The amorphous carbon system provides a critical test of the transferability of the potential, while the annealing simulations illustrate the graphitization process and test bond-making and bond-breaking. A wide spread of behavior is seen across the six potentials, with quantities such as sp2 fraction, radial distribution function, morphology, ring statistics, and 002 reflection intensity differing considerably. While none of the potentials is perfect, some perform particularly poorly. The lack of transferability can be traced to the details of the functional form, suggesting future directions in the development of carbon potentials. [1] C de Tomas, I Suarez-Martinez, NA Marks, Carbon 109, 681-693 (2016) [2] http://www.carbonpotentials.org

95

Heteroatom Doped Porous Carbons for Adsorption and Metal-free Catalysis

Wang, S. 1, Wenjie Tian1, Huayang Zhang1, and Sun, H.2


1 Department of Chemical Engineering, Curtin University, GPO Box U1987, Perth, WA 6845, Australia

2 School of Engineering, Edith Cowan University, Perth, Australia

Advanced oxidation processes (AOPs), utilizing a variety of oxidants such as H2O2, O3, or S2O8

2- to generate reactive radicals, can completely decompose organic pollutants in water into harmless substances, carbon oxide and water. For example, persulfate (S2O8

2-, PS) has been widely employed as an effective oxidant for degradation of organic compounds. Homogeneous catalysis using metal ions (Fe2+, Co3+), or heterogeneous catalysis with supported catalysts (Co, Ru) or metal oxides (α-MnO2, Co3O4) were applied to activate PS to produce reactive radicals. However, toxic heavy metal leaching is still unavoidable. The authors recently employed several metal-free catalysts such as chemically reduced graphene oxide (RGO), carbon nanotubes to activate peroxymonosulfate (PMS) or PS for phenol degradation. Scalable synthesis would further make the metal-free catalysis more appealing for the wide applications. To this end, in this study, glucose, an abundant and renewable carbon source derived from biomass is used with different N or S precursors for one-step synthesis of porous carbons. The high surface area, heteroatom (N or N-S) doping, combined with a 3D microporous structure make it a highly efficient metal-free catalyst for water remediation. The mechanism of the catalytic oxidation of an antibiotic sulfachloropyridazine (SCP) was also discussed. In addition, heteroatom (N or N-S) doped porous carbon were demonstrated to be excellent adsorbents for CO2 and SCP adsorption. This simple, green, and cost-effective protocol opens a new way for the large-scale production of high-quality metal-free catalysts for environmental remediation.

96

Heteroatom-doped carbon-based catalyst for efficient oxygen reduction

Li, Jincheng, Hou, Pengxiang, Liu, Chang, Cheng, Hui-Ming

[email protected]

Institute of Metal Research, Chinese Academy of Sciences, Shenyang, China

Developing low cost, highly active and durable electrocatalysts towards cathodic oxygen reduction reaction is one of the high-priority research directions for commercial application of low-temperature polymer electrolyte membrane fuel cells and metal-air batteries. Here we designed and synthesized a series of heteroatom-doped carbon-based catalysts with tailored active site, pore structure and electrical conductivity. A nitrogen-doped mesoporous carbon containing an embedded carbon nanotube (CNT) conductive network was prepared by CNT growth on silica nanoparticles, aniline polymerization and pyrolysis. A nitrogen-doped porous carbon microtube sponge was synthesized by one-step pyrolysis of facial cotton. Hierarchically porous iron-nitrogen-doped CNT was fabricated by depositing carbon and nitrogen sources on nanochannel of AAO template filled with iron salt, removing the template and final ammonia activation. These catalysts have a highly conductive CNT network and/or framework to improve electron transfer, high specific surface area and abundant pore structure enabling fast mass transport, and high content of heteroatom doping serving as active sites. These catalysts showed excellent ORR activity, with 20-30 mV more positive half-wave potential than that of commercial Pt/C catalysts in an alkaline medium.

97

Hierarchical porous carbon materials platform for energy and environmental applications

Luis Estevez1, Adam L Garcia1, Venkateshkumar Prabhakaran1, Jianming Zheng1,

Sookyung Jeong1, Brian Adams1, Wu Xu1, Priyanka Bhattacharya1, Xiaolin Li1, Yongsoon Shin1, Ji-Guang Zhang1

[email protected]

1 Pacific Northwest National Laboratory, Richland, WA USA

Herein, we present a strategy for a hierarchical porous carbon (HPC) material system with tunable textural properties and the ability to imbue porosity on all three different porosity regimes: micro- (<2 nm), meso- (2-50 nm) and macroporosity (>50 nm). We will show how optimization and modification of this strategy has resulted in HPCs with very large measured specific surface areas (>2500 m2/g via BET) combined with colossally high micro/mesopore volumes (~10 cm3/g)—the combination of which are rarely seen in porous carbon materials. We will show how we achieved these high textural characteristics via exquisite morphological control and how we were able to tune the carbon structure of the HPCs into either a hard carbon or a more ordered (graphitic) carbon. Furthermore, we will demonstrate how these HPCs can be utilized for energy storage applications by employing them as a scaffold-like materials platform on which to attach Si nanoparticles for lithium ion battery anodes. We will also demonstrate the advantage of the open morphology in our HPC materials in their use as supercapacitor electrodes and finally, we will demonstrate how our HPCs perform in environmental applications such as oil adsorption.

98

High Performance Carbon Nanotube Microstructure for Conversion Li-Ion Battery Anodes

de La Verpilliere, J1, George, C1, De Volder, M1, Boies, A1


1 University of Cambridge, Cambridge, United Kingdom

Beyond graphite and silicon, Li-ion battery anode materials relying on conversion reactions for Li ion storage have attracted tremendous academic interest due to their potentially high performances in terms of energy density, power density, cyclability, cost, and safety. Despite impressive progress in this field, novel materials are needed to minimise inherent drawbacks such as electrode pulverisation, voltage hysteresis, high reactivity towards commonly-used electrolytes, high first cycle irreversibility, or high operating voltages. We propose a novel carbon nanotube (CNT)-metal oxide hybrid microstructure synthesised using a known continuous aerosol-based process to address these issues. CNTs were grown radially from the surface of bimetallic Al-Fe oxide nanoparticles, forming octopus-like microstructures that were extensively characterised using both in-situ and ex-situ methods. Electrodes were then fabricated and tested in Li-ion coin cells in both half-cell and full cell configurations. We report the full electrochemical characterisation of these cells, including galvanostatic cycling, cyclic voltammetry, and electrochemical impedance spectroscopy, showing high performances in terms of capacity retention at high rates and over numerous of cycles. These good results are explained by (a) the unique composition of the core of these octopus-like structures, where Li ions are stored, which enhances the stability of the material towards the electrolyte as compared to pure iron oxide, and (b) the hierarchical CNT structure, with all CNTs interconnected via a central core and linking neighbouring particles, which enables efficient electron transport, heat dissipation, and mechanical CNT buffer effect to counteract the core’s volume expansion upon lithiation.

99

Highly efficient and selective adsorption of dyes onto halloysite/carbon

nanocomposites

Wu, X1, Tang, Y1, Zhang, X2, Wu, Y2 Presenting author’s e-mail: [email protected]

1 School of Chemistry and Chemical Engineering, Hefei University of Technology, Hefei

230009, China 2 School of Materials Science and Engineering, Hefei University of Technology, Hefei

230009, China

Halloysite/carbon adsorbents were prepared by one-step activation using ZnCl2 as activation agents, which has a micro-mesoporous structure with abundant functional groups. The adsorption of single dye and mixed dyes onto halloysite/carbon nanocomposites was investigated in this study. X–ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Transmission electron microscope (TEM), and Brunauer–Emmett–Teller analysis (BET) were performed to characterize the micro-structure of the obtained adsrobents, UV-Vis spectrophotometer (UV-Vis) was applied to detect the adsorption capacity of adsobents. The results showed that the fabricated halloysite/carbon had a specific high surface area with the value of 1969 m2/g. The halloysite/carbon showed selective adsorption for cationic dyes in which the adsorption capacity for malachite green and methylene blue reached 420mg/g and 408mg/g respectively. For the mixture of cationic and anionic dyes, halloysite/carbon also showed a highly selective adsorption for cationic dye resulting from the electrostatic attraction between halloysite/carbon and cationic dyes.

100

High-strength and Modulus Carbon Nanotube Fibers

Ok-Kyung Park1, Bon-Cheol Ku2


1 Carbon Composite Materials Research Center, Institute of Advanced Composite Materials, Korea Institute of Science and Technology (KIST), Jeonbuk, Korea

Among the carbon nanotube (CNTs)-based structural materials, carbon nanotube fibers (CNTFs) are very attractive materials in the high-performance composite industry due to their high mechanical properties, electrical conductivity, and low density. Despite the great properties of CNTs, a limitation in enhancing mechanical properties of CNTFs exists in the form of weak interfacial interactions between adjacent CNTs in the CNTFs. One promising approach to overcome this limitation is the introduction of cross-linking bonds between adjacent carbon shells.

Herein, we will present an effective novel method to make high-strength and modulus CNTFs via aryl radical cross-linking reactions. After aryl cross-linking reactions of CNTFs, the individual CNTs were cross-linked, which was confiremed by using Raman and XPS analysis. The mechanical properties were characterized by FAVIMAT (single fiber tester). The results showed that the cross-linking reaction of CNTFs can improve the mechanical properties of resulting CNTFs due to the interconnection of adjacent CNTs in the CNTFs. Compared to the pristine CNTFs, the tensile strength increased to 3.7 N/tex, and the modulus increased to 210 N/tex, i.e. enhancements of mechanical properties of approximately 130% and 350%, respectively. These results clearly confirm that the aryl cross-linking reaction is an effective method of developing mechanically strong CNTFs.

101

Hollow Carbon Nanotubes-Welded Carbon-Coated CoSe2 Nanospheres Polyhedron for Sodium Storage

Tang, Yongchao1, Zhao, Zongbin1, Hao, Xiaojuan2, Wang, Yuwei1, Liu, Yang1, Hou,

Yanan1, Yang, Qi1, Wang, Xuzhen1, Qiu, Jieshan1


1 Dalian University of Technology, Dalian, China

2 Commonwealth Scientific and Industrial Research Organization, Melbourne, Australia

Sodium ion batteries (SIBs) have re-emerged as promising alternatives to lithium ion batteries due to their good compatibility with environment, safety, and economy. Hitherto obtaining superior anode materials remains the bottleneck to real application. Herein, beginning with small ZIF-67 particles, via a nanoscale Kirkendall effect, non-destructive hollow polyhedral hybrids have been synthesized facilely, which are structured from carbon nanotubes (CNTs)-welded carbon-coated CoSe2 nanospheres (CoSe2@C/CNTs). With partial exhaustion of organic ligands, the proper growth of CNTs introduces additional mesopores and open channels into the hybrids, and avoids serious agglomeration of CoSe2 nanospheres. When employed as anode materials for SIBs with ether-based electrolyte, the CoSe2@C/CNTs shows overwhelmed merits over graphitic carbon-coated CoSe2 nanospheres polyhedral hybrids (CoSe2@GC) and bare CoSe2 particles. Specifically, the CoSe2@C/CNTs anode displays high reversible capacity (~470 mA h g-1 at 0.2 A g-1), good rate capability of ~373 mA h g-1 even at 10 A g-1, and eminent cycling stability of over 1000 cycles with a capacity retention of ~100% calculated from the 70th cycle. Electrochemical reaction dynamics analysis indicates the presence of considerable capacitive contribution during the discharge-charge cycles, which is beneficial to enhance the rate capability and cyclability of CoSe2@C/CNTs anode. Such results are mainly ascribed to the stable ether-based electrolyte-active materials intermediates, improved electrolyte-active materials contacts, and shortened charge transfer paths afforded by the unique hybrids nanostructure.

102

HOLLOW GRAPHENE SPHERE/Sno2 COMPOSITE AS ANODE MATERIAL FOR LITHIUM-ION BATTERIES

Zhao, D L, Gao, F, Cheng, X W, Ding Z W



The hollow graphene oxide spheres have been successfully fabricated from graphene oxide nanosheets utilizing a water-in-oil emulsion technique, which were prepared from natural flake graphite by oxidation and ultrasonic treatment. The hollow graphene oxide spheres were reduced to hollow graphene spheres (HGSs) at 500 ºC for 3 h under an atmosphere of Ar(95%)/H2(5%). Compared with the graphene sheets, the prepared hollow graphene spheres possess better cycle and high rate performances for the lithium storage, which thanks to the hollow structure, thin and porous shells consisting of graphene sheets. HGSs were dispersed into SnCl2 aqueous solution and was stirred at 30 °C for 1 h to obtain the HGSs suspension. The HGSs suspension was ultrasonicated and dried in a vacuum oven at 60 °C, thus HGSs/SnCl2 composite was obtained. The HGSs/SnCl2 composite was changed to HGS/SnO2 at 500 ºC for 1 h in the air. The first reversible specific capacity of HGS/SnO2 was as high as 975 mAh g-1 at a current density of 50 mAh g-1. Even at a high current density of 500 mAh g-1, the reversible specific capacity remained at 652 mAh g-1. After 50 cycles, the reversible capacity was still kept at 845 mAh g-1 at the current density of 50 mAh g-1. These results indicate that the prepared HGS/SnO2 possess excellent electrochemical performances for lithium storage. The high rate performance of HGS/SnO2 thanks to the hollow structure, thin and porous shells consisting of graphene sheets.

103

Hollow Porous Carbon Nanospheres/P Composite With Superior Na Storage Performance

Yao, S1, Cui, J1, Kim, J.K.1


1The Hong Kong University of Science and Technology, Clear Water Bay, Hong Kong, P. R. China

To satisfy the ever-growing demands of rechargeable battery market, sodium ion batteries (SIBs) have received much attention due to the abundant Na resource, low cost and similar electrochemistry of Na to Li.[1] Among many anode materials including SnO2

[2] and Sb2S3,[3] phosphorus (P) has been considered a promising candidate for SIBs owing to the ultrahigh theoretical specific capacity of 2596 mAh g-1 and a relatively safe working potential. Here, amorphous red P embedded in hollow porous carbon nanosphere (HPCNS/P) composites are synthesized as anode for high-performance SIBs. The anode delivers an admirable sodium storage capacity of ~ 1700 mAh g-1 at 0.1 A g-1 for over 300 cycles, and sustains equally excellent capacity retention over 76 % in the following 1000 cycles at 1.0 A g-1. The superior electrochemical performance can be attributed to the following ameliorating structural features: (i) hierarchical pores in HPCNSs not only provide enough space to host red P, but also enhance the electrolyte permeation and Na+ ion transport; (ii) the red P active materials are fully encapsulated within the mesopores of core/shell structured HPCNSs; (iii) the chemical bonds present between the HPCNS carbon shell and red P ensure excellent contacts for efficient utilization of the active material and facilitate fast electron/ion transport; (iv) the large volume change of red P occurring during charge/discharge cycles are effectively confined within the hollow core by the robust HPCNS shell without structural damage or pulverization, as proven by the in situ TEM examination. [1] J. Cui, S. Yao, J.K. Kim, Recent progress in rational design of anode materials for

high-performance Na-ion batteries, Energy Storage Mater. (2017). doi:10.1016/j.ensm.2016.12.005.

[2] J. Cui, Z.L. Xu, S. Yao, J. Huang, J.Q. Huang, S. Abouali, M. Akbari Garakani, X. Ning, J.K. Kim, Enhanced conversion reaction kinetics in low crystallinity SnO2/CNT anodes for Na-ion batteries, J. Mater. Chem. A. 4 (2016) 10964–10973.

[3] S. Yao, J. Cui, Z. Lu, Z.L. Xu, L. Qin, J. Huang, Z. Sadighi, F. Ciucci, J.K. Kim, Unveiling the unique phase transformation behavior and sodiation kinetics of 1D van der Waals Sb2S3 Anodes for sodium ion batteries, Adv. Energy Mater. (2017) 1602149.

104

Honeycomb Carbon Monoliths from Brown Coal

Parsa, M1 and Chaffee, AL1

E-mail: [email protected]

1 Monash University, Victoria, Australia

A novel method for preparing the carbon honeycomb monoliths (HMs) directly from Victorian brown coal (VBC) has been developed. The approach builds upon prior research that developed robust monolithic structures, but without channels, by extrusion of kneaded VBC to give a dewatered product known as ‘densified coal’. In the present case, however, the monoliths are further transformed into monolith active carbon products with a wide range of potential applications for both gas and liquid phase adsorption, as well as in catalysis and as electrode materials. The active carbon monoliths have high cell density (around 470 cells/cm2), are structurally robust and possess high surface areas (>850 m2/g). The HM form of active carbon offers a number of advantages over conventional powdered or pelleted analogues. The pressure drop across a ‘fixed bed’ of the material is substantially reduced enabling higher throughput. For gas phase adsorption applications at least, the adsorbed component(s) can be very quickly recovered and the HM regenerated by facile application of electrical current to the monolith. This is referred to as electrical swing adsorption (ESA) and, though it resembles conventional thermal swing adsorption (TSA), it provides the possibility of higher per cycle productivity. Another advantage of ESA is that by providing the energy required for desorption ‘in situ’ (by Joule heating) rather than by heat exchange from a gas stream containing other ‘diluting’ components, the gas recovered in each cycle is relatively pure. Optimised ESA cycles may be simpler, involve fewer steps and/or require less intensity (e.g. reduced cooling).

105

High Energy Hybrid Capacitors in Neutral Aqueous Electrolytes with Asymmetric Carbon Electrodes

Przygocki P., Abbas Q., Béguin F.,

[email protected]

Poznan University of Technology, Berdychowo 4, 60-965 Poznan, Poland In the last years, we have demonstrated that eco-friendly neutral aqueous solutions, e.g., 1 mol L-1 Li2SO4 are attractive electrolytes for the development of eco-friendly and high energy electrochemical capacitors (ECs), with voltage values as high as 1.5 V [1]. Such good properties are owing to the production of hydroxyl anions in the porosity of the negative carbon electrode, which consequently leads to downshifting the electrode potential (according to the Nernst law) [2]. Based on the implementation of neutral aqueous electrolytes, the presentation will introduce hybrid carbon/carbon SCs involving an electrical-double layer (EDL) negative electrode and a battery-type positive one containing confined polyiodide species in its porosity. The conditions of polyiodides confinement will be presented together with the identification of materials by Raman spectroscopy, nitrogen adsorption at 77K and thermoprogrammed desorption. The electrochemical measurements on the hybrid cell demonstrate the possibility to reach 1.5 V while doubling capacitance as compared to a symmetric EDL carbon/carbon cell [3]. The performance was improved by using carbons of different porosity for polyiodides confinement and hydroxyl anions trapping. Such construction enabled to approach the energy density of EDL capacitors in organic electrolyte. Moreover, ECs could be operated down to -40°C by introducing a new type of neutral aqueous electrolyte, which quenches the hydrogen storage mechanism at the negative electrode. This novel system presents most advantages of EDLCs in organic electrolyte without detrimental aspects related with possible safety hazards. Acknowledgements: Narodowe Centrum Nauki (NCN) is acknowledged for supporting the OPUS project UMO 2014/15/B/ST4/04957. References:

1. P. Ratajczak, K. Jurewicz, P. Skowron, Q. Abbas, F. Béguin, Electrochim. Acta 130

(2014) 344.

2. Q. Gao, L. Demarconnay, E. Raymundo, F. Béguin, Energy Environ. Sci., 5 (2012) 9611.

3. Q. Abbas, P. Babuchowska, E. Frackowiak, F. Béguin, J. Power Sources, 326 (2016) 652.

106

Hybrid Nanostructures for Lithium and Sodium Storage

Zaiping Guo*1,2

1. Institute for Superconducting & Electronic Materials, University of Wollongong, NSW

2522, Australia 2. School of Mechanical, Materials, and Mechatronic Engineering, University of

Wollongong, NSW 2522, Australia

* [email protected] Energy storage is an important issue to realize low carbon society and there have been many challenges. Lithium ion batteries and sodium ion batteries are particularly attracted attention of scientists and engineers as promising devices. Materials engineering plays a key role in the field of battery research. In particular, engineering materials at the nanoscale offers unique properties resulting in high performance electrodes in various energy storage devices. Consequently, considerable efforts have been made in recent years to fulfil the future requirements of electrochemical energy storage devices. Various multi-functional hybrid nanostructured materials are currently being studied to improve energy and power densities of next generation batteries. In this talk, I will present some of our recent progress in the synthesis of different types of hybrid nanostructures to enhance the electrochemical energy storage properties of Li-ion battery and sodium-ion battery.

107

Improving thermal-shock resistance of SiC-coated C/Cs with ferrocene refined SiC

Huo C., Guo L., Li H., Wang C., Zhang Y.



To improve the thermal shock resistance of SiC coatings applied on carbon/carbon (C/C) composites, ferrocene ((C5H5)2Fe) was introduced in the coatings during the pack cementation process. The microstructure and thermal shock resistance of modified SiC coating were studied. The HNO3 treated carbon fiber and the introduction of (C5H5)2Fe could raise the nucleation point and the decomposition of (C5H5)2Fe can slow down the sintering process, which helps to decreased the sizes of SiC particles and micro-defects (including micro-cracks and miro-holes). Thermal shock test revealed that the mass change rate of C/C composites decreased from 18.25% to 10.08% after thermal cycle test between 1773 K and room temperature for 25 times, suggesting a better shock resistance for the modified SiC coating compared with the base coatings (without modification). This work provides a novel way to modify the SiC coating capable of releasing the thermal residual stress and decreasing the oxygen diffusion channels and then further increasing the thermal shock resistance of C/C composites without other supplementary protective coatings.

108

Influence of damage effects on the mechanical properties of C/C

Behnisch, T.1, Thieme, M.1, Böhm, R.1, Gude, M.1


Institute of Lightweight Engineering and Polymer Technology, Technische Universität Dresden, Dresden, Germany

Carbon fibre reinforced carbon (C/C) is a composite material with high temperature resistant properties. Because of its high weight specific rigidity and strength as well, C/C is preferably used for complex loaded high temperature applications. The structural design of C/C is characterized by stacked textile layers with a bidirectional orientation of the carbon fibres. Therefore this composite material presents good in-plane properties and the material behaviour is well predictable by the development of a variety of material models in the last years. Due to a comparatively material intrinsic high porosity caused by occurring cracks and outgassing during the high temperature manufacturing process, C/C is compressible under local out-of-plane compression load. With increasing upsetting deformation under local compression damage effects occur and these results in a significant degradation of the mechanical properties. The influence of this out-of-plane damage on the in-plane behaviour of C/C is absolutely not addressed in material modelling. But this leads to an overassessment of the structural strength as well as the load capability of C/C-components. This paper shows an in-situ investigation of the inner material micro structure during the operating compression load. Using X-ray computer tomography and optical micro section analysing the out-of-plane damage effects will identify. Further a modified material damage model to observe the impact of out-of-plane compression loading on the in-plane material behaviour is provided.

109

Interlayer Defects In Aa-Stacked Bilayer Graphene

A. Vuong1, T. Trevethan1, C. D. Latham2, C. P. Ewels3, D. Erbahar4, P.R. Briddon5, M. J. Rayson5, M. I. Heggie2


1 University of Surrey, Guildford, United Kingdom 2 University of Loughborough, Loughborough, United Kingdom

3 Université de Nantes, Nantes, France 4 Gebze Technical University, Kocaeli, Turkey

5 Newcastle University, Newcastle upon Tyne, United Kingdom

In AA stacking all atoms are in registry in the direction perpendicular to the layers. This can occur when graphene folds to make a bilayer or, in an approximate sense, in rotated layers with a small angle of relative rotation. In previous work, it has been shown that vacancies can bind to each other across the interlayer gap in graphite, and also that some patterns of aggregation must arise where the bonds so formed between vacancy aggregates in different layers give rise to a ramp of graphene connecting graphene layers together. Here we present the results of ab initio Density Functional Theory calculations of complexes of various morphologies that are formed from the binding of vacancy oligomers across neighbouring layers in AA stacked bilayers. As with AB stacking, the carbon atoms surrounding lattice vacancies can form interlayer structures with sp2 bonding that are lower in energy than in-plane reconstructions. The sp2 interlayer bonding of adjacent multi-vacancy defects in registry creates a type of stable sp2 bonded 'wormhole' or tunnel defect between the layers. We also identify a new class of 'mezzanine' structure characterised by sp3 interlayer bonding, resembling a prismatic vacancy loop. The hexavacancy mezzanine variant, i.e. V6 arising from V3 in each layer, has six sp3 carbon atoms sitting midway between the two carbon layers which each bond to both layers. It is substantially more stable than other vacancy aggregates obtainable by vacancy addition at temperatures where Stone-Wales transformations cannot occur.

110

Intriguing role of sulphur in enhancement of carbon-based electrochemical capacitors

Fic, K, Meller, M, Frackowiak, E


Poznan University of Technology, Poznan, Poland

Several forms of activated carbons have already been implemented and widely investigated as electrodes for electrochemical capacitors. Aqueous solutions based on inorganic salts demonstrated effective operating voltages around 1.6 V, and several interesting strategies have been furthermore implemented to improve these systems, including redox activity of the electrolyte.

This work is focused on the electrochemical performance of the activated carbon electrodes operating in various electrolytes containing sulphur-based species. Since sulphate (SO4

2-)-based aqueous solutions have already been widely investigated, this study will discuss the electrolytes with containing S2O3

2-, SO32- and S2- anions and their interaction with a carbon

electrode. The results obtained clearly indicated that sulphur plays an important role in the charge accumulation process and has an excellent redox chemistry. Dependently on the electrolyte pH, the ionic specimen might be easily reduced or oxidized and perfectly preserves the activated carbon surface against oxidation. Moreover, the affinity of sulphur to the carbon surface promotes a sulphur-carbon bonding and creates additional redox active site on the electrode surface.

A variety of electrochemical methods used in the study confirmed that a specific formulation of the electrolyte with sulphur-based redox shuttle might remarkably enhance the electrode capacitance (up to 300 F g-1) and the operating voltage (up to 2.0 V). Moreover, operando Raman spectroscopy proved that sulphur-carbon bond is reversibly created while the charge transfer occurs. Furthermore, high energy density (ca. 26 Wh kg-1) maintained at excellent power rates (1 kW kg-1) has been preserved during 10 000 charge/discharge cycles with reversibility of 97%.

111

Investigation of chemical states of nitrogen introduced to fullerene-soot-derived onion-like-carbons and its property toward oxygen reduction reaction

Ishii, T1, Maie, T1, Nariduka, K1, Kannari, N1, Takigami, M1, Ozaki, J1


1 Gunma University, Kiryu, Japan Nitrogen doped carbons are some of the most promising candidates for cathode catalysts in polymer electrolyte fuel cells. To be developed as high performance catalysts, it is important to identify the active sites of nitrogen doped carbons for oxygen reduction reaction (ORR). Pyridinic structures have been reported as one of the candidates for the active sites. However, chemical states of nitrogen are complicated and still be under debate because their states are affected not only by the chemical structure of nitrogen but also by many factors, such as defects and a curvature of graphene sheets. In this study, nitrogen doped onion-like carbons (N-OLCs) derived from fullerene soot were prepared as a model material for defects and/or curvature induced nitrogen doped carbons. N-OLC shows corrugated graphitic layers on the surface, which was obtained by a heat-treatment of pristine OLC in NH3 atmosphere. The chemical states of nitrogen formed on N-OLCs were further investigated by using X-ray photoelectron spectroscopy, high-temperature temperature-programmed-desorption and quantum chemical calculation. These unusual but effective techniques suggested that the curvature of graphene sheets enhances the activity of nitrogen spices toward ORR.

112

Investigations of The Adsorption of Volatile Organic Compounds onto Activated Carbon Using 1h NMR

Le Bozec, G1, Giraudet, S1, Le Polles, L1, Le Cloirec, P1

[email protected]

1 Ecole Nationale Supérieure de Chimie de Rennes, CNRS, UMR 6226, Rennes, France

Three volatile organic compounds (VOC), namely benzene, cyclohexane, dichloromethane, were adsorbed onto an activated carbon fiber cloth. 1H (magic angle spinning, MAS, and pulse field gradient, PFG) nuclear magnetic resonance (NMR) techniques were carried out and the signals were analysed in terms of peak surface areas and shifts. On one hand, the MAS NMR was shown to be very useful for determining the intrinsic quantification of adsorbed molecules (VOC and/or water) in the porosity of the adsorbent. Using an external calibration, the adsorption capacities ranged from 0.2 to 4 mol.kg-1 depending on the residual gas-phase concentration and the humidity of the sample. Moreover, the mechanisms of interactions between adsorbed organic molecules and the carbon walls were evidenced. The positions of the adsorbed molecules inside the pore volume are proposed; the proton-wall distance was less than 0.15 nm. This observation was obtained from the chemical shift in NMR spectra and was confirmed by the pore size distribution of the adsorbent. Finally, PFG NMR was used to assess the diffusivities of VOC inside the porous structure. From these experiments, a single diffusivity was determined for each VOC, with orders of magnitude, which correspond to surface diffusion. Indeed, surface diffusion coefficients (DS) were estimated at approximately 4.10-12 m2.s-1 for cyclohexane, 1.10-11 m2.s-1 for benzene and 4.10-11 m2.s-1 for dichloromethane. In order to approach the macroscopic diffusivities, that could be used in kinetic models for instance, longer times of observation in PFG measurements should be used.

113

ION Storage Properties of Metal-Organic Frameworks Deposited on Nanocarbon Surfaces

Ishii, Y, Taniguchi Y, Nakamura, M, Kawasaki, S


Nagoya Institute of Technology, Nagoya, Japan

Rechargeable Li-ion batteries (LIBs) have been used as a major power source of portable electric devices because they have superior energy density compared to other energy storage devices such as lead-acid batteries, nickel-hydride batteries, and electric double layer capacitors (EDLCs). In addition to the classical small-scale applications, LIBs are also used for large scale systems such as electric vehicles, renewable energy storage, and peak-shaving in recent days. However, low temperature performance of LIB is not enough especially at T < 0°C. In order to increase the low-temperature performance of LIBs, developments of new electrode materials are required. In the present study, we report that metal-organic framework (MOF) nanoparticles having 3D ion-diffusion path way shows good alkaline-ion (Li, Na, K) storage properties even at low-temperature conditions. Furthermore, we also report that the performance of MOFs is further improved by using nanocarbon materials, such as carbon nanofiber, single-walled carbon nanotubes, and graphene. In this study, we prepared several kinds of MOC-nanocarbon composites by a simple electrochemical method. Thin MOF layer (~100 nm) was successfully deposited on the surface of nanocarbons. By using nanocarbon materials, ionic/electronic transport kinetics were dramatically improved, and the MOF/nanocarbon composites can store lithium-ion very smoothly even at −40°C. In order to clarify the reason why the composite electrode works well even at extremely low-temperature condition, electrochemical impedance measurements were performed at various temperatures. We will discuss the role of electrode nanostructure from a kinetic point of view.

114

Ionic Liquid Sizing Agents for High Performance Carbon Fiber Composites.

Henderson, L. C.,1 Servinis, L., 1 Beggs, K. M., 1 Eyckens, D. J., 1 Walsh, T. R., 1 Demir, B. 1


1 Deakin University, Institute for Frontier Materials, Carbon Nexus, Geelong, Victoria, Australia, 3216

Carbon fibre composites are considered a key material for the future. These consist of plastics which have been reinforced with the carbon fibres in a woven or unidirectional pattern and represent a major weapon in the fight against CO2 emissions. Despite their promise, the Achilles heel of carbon fibre composites is the fibre-to-matrix interface which largely dictates the ultimate performance of the composite material, as a typical mode of failure fibre pull out. All carbon fiber is manufactured in the same way and the only attempt to make a fibre compatible with the intended polymer is to coat the fibres in a thin (~0.3 μm) layer of polymer which is derived from the same family as the intended matrix. In this work we combine the surface modification of carbon fibres and the use of ionic liquids (imidazolium derived and solvate ionic liquids) as alternative sizing agents and examine the effect on fibre-to-matrix adhesion. We observe an unusual synergism between these two approaches leading to an interfacial shear strength increase of >350%. This result has been attributed to two effects (i) cross-linking of the surface bound functionalities to the epoxy resin – generating a physical link between fibre and resin, and (ii) a localized plasticizing effect generated by the ionic liquid in the epoxy matrix.

Examination of the interface using molecular dynamics simulations suggests that one of the ionic liquids (BmimCl) aggregates on the fibre surface and, being insoluble in the liquid polymer precursor, aggregates within the final crosslinked network. This creates pockets of IL-filled micro-domains, which we suggest plasticize the polymer and possibly allow for energy dissipation via deformation at the fibre to matrix interface.

Figure 2 Left: Molecular dynamics simulation showing the aggregation of IL in the functionalized composite (polymer not shown for clarity); Right: Interfacial Adhesion using Ionic Liquids Sizing (UF=

unfunctionalized fibre; F= Amine-Functionalised Fibre

Unsized Sized UF+G3TFSA UF+BmimCl F+G3TFSA F+BmimCl

0

30

60

90

IFS

S (

GP

a)

Fibre Type

115

Joule Heated Carbon Microtube CVD Reactor

Luchnikov, V1, Saito, Y2, Ghimbeu, C1


1 Institut de Science des Matériaux de Mulhouse,CNRS , Mulhouse, France 2 The University of Tokyo, Japan.

We propose a new kind of a joule heated, low power consumption micro-scale chemical vapor deposition (CVD) reactor, which consists of a carbon microtube, derived from a scroll of chitosan, a cheap semisynthetic biopolylmer [1]. The precursor scrolls are formed via spontaneous rolling caused by in-plane stresses in the chitosan films. Heating of the scrolls in inert nitrogen atmosphere up to 700°C converts them into electrically conductive amorphous carbon tubes, which have almost perfect hollow-core cylinder shape. The inner diameter of the tubes depends on the thickness of the precursor films and can be varied in the limits from few microns to few hundreds of microns. Joule heating improves conductivity of the tubes due to partial graphitization of amorphous carbon. The so-formed confined space CVD microreactors, powered by electrical current, can be easily loaded by catalytic micro/nanoparticles via the particles deposition onto the precursor films prior to rolling [2,3]. Small size of the reactor enables its good reactivity to the variations of the applied voltage due to small thermal inertness and effective radiative cooling. This allows realizing complex heating kinetics via computer-guided power supply, coupled with high-temperature pyrometer control. [1] Y. Saito, V.A. Luchnikov, A. Inaba, K. Tamura, Carbohydr. Polym. 2014, 109, 44 [2] V.A. Luchnikov, Y. Saito, L. Tsanis, Macromol. Rapid Commun. 2012, 33, 1404. [3] C.M. Ghimbeu, A.I.Egunov, A.S.Ryzhikov, V.A. Luchnikov, J. Mater. Sci. Technol. 2015, 31, 881.

116

Shear Alignment of Nematic Phase Graphene Oxide: A mass-producible technique for fabricating large-area graphene-based membranes with nanofiltration properties

Abozar Akbari and Mainak Majumder.


Department of Mechanical and Aerospace Engineering, Nanoscale Science and

Engineering Laboratory (NSEL), Monash University, Clayton, Victoria 3800,.

Graphene-based membranes demonstrating ultra-fast water transport, precise molecular sieving of gas and solvated molecules, have been considered for a host of applications in desalination, gas separation and pervaporation; however scale-up of these membranes to large-areas remains an unresolved problem. Here we are going to present that the discotic nematic phase of graphene oxide (GO) can be shear aligned to form highly ordered, continuous, thin films of multi-layered GO on a support membrane by an industrially-adaptable method to produce large-area in less than 5 seconds1. The pseudoplastic, shear thinning fluid of the nematic phase of GO promotes membrane formation by enhancing wetting and spreading at high shear rates, while resisting dewetting at low shear rates. Pressure driven transport data demonstrate high retention (> 90%) for charged and uncharged organic probe molecules with a hydrated radius above 5 Å as well as modest (30-40%) retention of monovalent and divalent salts. The highly ordered graphene sheets in the membrane plane make organized channels and enhance the permeability of the membrane (71 ± 5 l m-2 hr-1bar-1 for 150 ±15 nm thick membranes). Benchmarking experiments with a highly established commercial nanofiltration membrane demonstrate around 9 times higher water flux at comparable retention values and excellent flux recovery by chemical cleaning. 1. Akbari A, Sheath P, Martin ST, Shinde DB, Shaibani M, Banerjee PC, et al. Large-

area graphene-based nanofiltration membranes by shear alignment of discotic nematic liquid crystals of graphene oxide. Nat Commun 2016, 7.

117

Low Temperature Adsorption-based Isotope Gas Separation using Nanoporous Carbons

Kumar, S1, Fernando, V –B1, Ito, H2, Futamura, R1 and Katsumi, K*1


1 Shinshu University, Center for Energy and Environmental Science, Nagano, JAPAN 2 Toyohashi University of Technology, Department of Environmental and Life Sciences,

Toyohashi, JAPAN

Isotopes separation is crucial for various advanced technologies including isotope labelling, renewable energy, nuclear power & medical diagnostic applications. However, their nearly identical chemical properties make the separation challenging. The low productivity and large energy costs involved in the present fractional distillation based separation of molecules hinders the relevant applications. Recently, Porous materials have been extensively studied for adsorption based separation of light isotope molecules. Our group has studied quantum molecular sieving effects of various nanoporous materials for H2/D2 isotope couple with experimental and quantum simulation techniques [1-3]. Furthermore, we have also studies quantum molecular sieving effect of activated carbon fibers on methane isotopes 12CD4 and 12CH4, which can be applied to separate huge amount of radioactive waste produced from graphite based nuclear plants [4]. Here, we have studied new selective adsorption of heavier oxygen isotopes at low temperature. The selectivity shows high dependence on the pore size, temperature and dosing pressure. Such selective adsorption of oxygen isotopes will bring advancements in biomedical applications particularly Positron Emission Tomography (PET) imaging technique which can be used to detect abnormalities that other imaging techniques may not detect [5]. 1. S. Niimura et al., J. Am. Chem. Soc. 2012, 134, 18483. 2. H. Kagita et al., J. Phys. Chem. C. 2012, 116, 20918. 3. H. Tanaka et al., J. Am. Chem. Soc. 2005, 127, 7511. 4. D. Minami et al., Carbon 2014, June 29-July 4, Jeju, Korea. 5. T. Rudroff et al, J Appl Physiol. 2015, 118, 1181.

118

Low-Dimensional Nano-Carbons: Form Doped Graphene to Biological Applications of Nanotubes

Mauricio Terrones1


1Department of Physics, Department of Chemistry, Department of Materials Science and Engineering and Center for 2-Dimensional & Layered Materials. The Pennsylvania State University, University Park, Pennsylvania 16802, USA & Institute of Carbon Science and

Technology, Shinshu University, JAPAN

This talk will discuss the synthesis of large-area, high-quality monolayers of nitrogen-, silicon- and boron-doped graphene sheets on Cu foils using ambient-pressure chemical vapor deposition (AP-CVD). Scanning tunneling microscopy (STM) and spectroscopy (STS) reveal that the defects in the doped graphene samples arrange in different geometrical configurations exhibiting different electronic and magnetic properties. Interestingly, these doped layers could be used as efficient molecular sensors and electronic devices. In addition, the synthesis of hybrid carbon materials consisting of sandwich layers of graphene layers and carbon nanotubes by a self-assembly route will be discussed. These films are energetically stable and could well find important applications as field emission sources, catalytic supports, gas adsorption materials and super capacitors. We will describe the synthesis of carbon nanotubes and nanotube networks using different dopants during chemical vapor deposition. In particular, the effects of sulfur, boron and nitrogen will be discussed. For example, sulfur induces the formation of pentagons and heptagons, whereas boron aids the growth of heptagonal carbon rings, and nitrogen promotes the formation of pentagonal cusps. It will be demonstrated that it is indeed possible to assemble/grow carbon nanotube networks if a careful control of dopants is achieved during chemical vapor deposition (CVD) growth. High resolution electron energy loss spectroscopy (HR-EELS) studies on these nanotube materials will be presented, and the locations of boron, sulfur and nitrogen within nanotubes will also be shown. First principles theoretical calculations on nanotubes containing pentagon, hexagons and heptagons in the presence of these dopants will be discussed. Recent experiments on the synthesis of large area super-tough smart carbon textiles, capacitors, catalysts and more. We will also discuss the citotoxicity and applications as molecular sensors and virus traps of these doped nanocarbons. Finally, different routes to synthesize 3D architectures of covalently interconnected carbon nanotubes will also be discussed. These include the use of Si an atomic welder and a multi-stage CVD growth on crisscross nanotubes decorated with Fe nanoparticles. Physico-chemical properties of these novel architectures will also be introduced.

119

Mechanical and electromagnetic shielding performance of carbon fibre reinforced multilayered (PyC-SiC)n matrix composites

Kezhi Li 1, Yan Jia1


1 Northwestern Polytechnical University, Xi’an, P.R. China

Carbon fibre reinforced multilayered pyrocarbon-silicon carbide ((PyC-SiC)n) matrix (C/(PyC-SiC)n) composites were prepared by alternate deposition of PyC and SiC inside preforms via chemical vapour infiltration. Effects of the number of PyC-SiC sequences (n=1, 2 and 4) on matrix microstructure, static and dynamic mechanical properties, electrical conductivity and electromagnetic interference (EMI) shielding performance of C/(PyC-SiC)n composites were investigated. The results show that the matrices of three composites possess two-layer, four-layer and eight-layer microstructure consisting of PyC and β-SiC, respectively. With increasing the number of sequences, flexural strength and fracture toughness of the composites increase from 121 ± 17 to 193 ± 18 MPa and from 3.0 ± 0.1 to 4.2 ± 0.3 MPa m1/2. The enhanced static mechanical properties of C/(PyC-SiC)n composites are attributed to the increasing number of interfaces, supplying more channels for crack deflection and propagation, which is favourable to fracture energy dissipation. Moreover, with the increase of sequences number, the internal friction increases under different testing conditions (frequency and strain amplitude) due to the enhancement of interfacial internal friction. The total shielding effectiveness (SE) of the composites increases from 34 to 42 dB in the frequency range of 8.2–12.4 GHz with the increase of PyC-SiC sequences number due to the increasing electrical conductivity and polarization of the multilayered matrix. The high EMI SE combined with low density and good mechanical properties of C/(PyC-SiC)n composites exhibit great potential as lightweight and high-performance structural and functional materials.

120

Mechanically Activated Carbon Textile via Chemistry of Metal Extraction

Lam, D. V.1,2, Hwangbo, Y.1, Kim1,2, Kim, K.-S.1, Jang, B.1, Kim, J.-H. 1,2 , S.-M. Lee1,2


1Department of Nanomechanics, Korea Institute of Machinery and Materials (KIMM), 156

Gajeongbuk-ro, Yuseong-gu, Daejeon 34113, South Korea 2Nano Mechatronics, Korea University of Science and Technology (UST), 217 Gajeong-ro,

Yuseong-gu, Daejeon 34103, South Korea

Carbothermic reduction in the chemistry of metal extraction (MO(s) + C(s) → M(s) + CO(g)) using carbon as a sacrificial agent has been used to smelt metals from diverse oxide ores since ancient times. Here, we paid attention to a new aspect of the carbothermic reduction remained unnoticed till now to prepare activated carbon textile for high rate-performance supercapacitors. On the basis of thermodynamic reducibility of metal oxides reported by Ellingham, we employed not carbon, but metal oxide as a sacrificial agent in order to prepare activated carbon textile. We conformally coated ZnO on bare cotton textile using atomic layer deposition (ALD), followed by pyrolysis at high temperature (C(s) + ZnO(s) → C’(s) + Zn(g) + CO(g)). We figured out that it leads to concurrent carbonization and activation in a chemical as well as mechanical way. Particularly, the combined effects of mechanical buckling and fracture occurred between ZnO and cotton were turned out to play an important role in carbonizing and activating cotton textile, thereby significantly increasing surface area (nearly 10 times) compared with the cotton textile prepared without ZnO. The carbon textiles prepared by carbothermic reduction showed impressive combination properties of high power and energy densities (over 20 times increase) together with high cyclic stability.

121

Mechanochemical Suzuki polycondensation - from linear to porous carbonaceous polymers

Grätz, S1, Wulfrum, B1, Borchardt, L1


1 Technische Universität Dresden, Dresden, Germany

In the recent past, mechanochemical reactions have climbed their way back into general chemistry. As a green and sustainable method, the future of this field is very promising since the use of toxic solvents can be avoided and selectivities and yields are generally high. Bypassing solubility issues and offering the perks of a solid-state reaction, mechanochemistry is a versatile method for material synthesis. By introducing the concept of a Suzuki polycondensation into the mechanochemical environment, we have been able to synthesize linear poly(phenylenes) with larger polymerization degrees than possible by any other conventional solution processes. An in-depth study, of the different milling parameters (milling material, time, catalyst concentration and monomer type), was undertaken using the linear system as a model. Utilizing an advanced milling setup, it was possible to record the pressure and temperature development in situ during the milling process and thereby gaining a deeper insight into the reaction mechanism. Furthermore, we applied the obtained knowledge to tri- and tetra-functional monomers and consequently synthesized a series of different carbonaceous 3D-polymers. Summing up, we transfered the classical wet chemical process of a Suzuki-polycondensation into a solvent-free environment, removing the need of soluble precursors and special palladium ligands in the process. The obtained polymers show a defined structure and the solid-state reaction is proceeding swiftly reaching high yields after only 30 minutes. The wide scope of application, e.g. the synthesis of graphene nano-ribbons and nano-platelets, is rendering our approach as a sustainable and fast alternative to established methods.

122

Mesoporous activated carbon with ultrahigh specific surface area for Supercapacitors

Rongwei Yan, Bo Hou, Lihong Yin, De Li, Shuo Yang, Yong Chen*


State Key Laboratory of South China Sea Marine Resource Utilisation, Hainan Provincial Key Laboratory of Research on Utilization of Si-Zr-Ti Resources, Hainan University,

570228 Haikou, China

Supercapacitors have become increasingly popular due to their high power density, excellent cycle stability. Currently, the most electrode materials of commercial supercapacitors are activated carbon due to the high specific surface area, large pore volume with the easy tuning pore size and low cost. The energy storage density of supercapacitors is highly depended on electrostatic adsorption at the electrode/electrolyte interface. Hence, both the specific surface area and the pore size distribution are essential in the capacitance performance of electrode materials. It has been demonstrated that pore size less than 1 nm may obviously enhance the specific capacitance, whereas micropore size smaller than 0.5 nm is insufficient to form a double layer The suitable pore size should be slightly larger than the ion size of the electrolyte. Also, it was found that mesopores could promote electrolyte diffusion, leading to improvement in the power density. Coconut shells are conventional raw materials to prepare activated carbon for supercapacitors, due to their unique natural structure, high carbon content and low ash content. However, their pore size diameters are difficult to adjust to meet the growing demand for supercapacitors. In this study, the mesoporous activated carbon with improved capacitive properties from coconut shells through low-temperature carbonization and KOH activation process. At the optimum preparation conditions, the highest specific surface area up to 4072 m2 g-1 was obtained.

123

Metallic-like carbon nanosphere qubits

Choucair, M1, Nafradi, B2


1 University of Sydney, Sydney, Australia 2 Ecole Polytechnique Fédérale de Lausanne, Lausanne, Switzerland

Our experimental results demonstrate the feasibility of operating electron spins in conducting carbon nanospheres as quantum bits at room temperature. Following the observation of spin polarisation by electron spin resonance, we control the quantum state of the electron spin by applying short bursts of an oscillating magnetic field and observe coherent oscillations of the spin state. We show that the electron spin lifetime exceeds the prerequisite for applications in spintronics and quantum information processing. This was possible through electron confinement to the nanometre-sized, non-crystalline yet metallic-like carbon spheres. This work effectively bridges the disparate research directions in the fields of inorganic and molecular materials for electron spin qubits and has broad applicability: spin qubits can now be manipulated at room temperature without the need for isotopically engineering a host material, diluting the spin-carrying molecule, cryogenic temperatures, the preparation of well-defined crystal structures, or the use of metals. The facile preparation of a carbon material using common laboratory reagents, combined with the use of well-established electron spin manipulation measurements at room temperature, effectively reduces many of the technological barriers to realising practical quantum computing and spintronics using solid-state materials. The material can be readily chemically processed and it is prepared in a form suitable for device processing: we have demonstrated that the conducting nanospheres can be isolated on a silicon surface by physically manipulating individual nanospheres which may provide an initial avenue to high density qubit arrays of nanospheres that are integrated onto existing silicon technologies or thin-film-based electronics

124

Metal–organic-framework-derived formation of Co-N-doped carbon materials for efficient oxygen reduction reaction

Tian, H.1, Liu, J.1, Liu, S. M.1


1 Curtin University, Perth, Australia

Non-precious metal nitrogen-doped carbonaceous materials have attracted tremendous attention in the field of electrochemical energy storage and conversion. Heroin, we report the designed synthesis of a novel series of nitrogen doped cobalt/carbon nanocomposites and their evaluation of electrochemical properties. Novel yolk-shell structured Co nanoparticles@polymer materials are fabricated from the facile coating polymer strategy on the surface of ZIF-67. After calcination in nitrogen atmosphere, the cobalt/N/C nanocomposites in which cobalt metal nanoparticles are embedded in the highly porous and graphitic carbon matrix are successfully achieved. The cobalt nanoparticles containing cobalt metal crystallites with an oxidized shell and/or smaller (or amorphous) cobalt-oxide deposits appear on the surface of graphitic carbons. The prepared Co-N-C nanoparticles showed favorable electrocatalytic activity of oxygen revolution reactions, which is attributed to its high graphitic degree, large surface area and the large amount existence of Co-N active sites.

125

Metal-polydopamine framework derived hollow Carbon Particles for Electrocatalysis

Liang Y1, Wei J2, Hu Y.X1, Chen X.F1, Zhang J3. Zhang X.Y1, Jiang S.P3, Tao S.W1, Wang H. T1


1 Monash University, Melbourne, Australia 2 XI’AN Jiangtong University, XI’AN, China


Hollow carbon nanoparticles with tuneable size and composition are attractive for developing efficient electrocatalysts. However, to satisfy different applications, extra functional procedures are normally needed, such as introducing heteroatoms into hollow carbon particles. Herein, we demonstrate a “Metal-organic frameworks (MOFs) genetic” strategy to synthesize hollow metal-organic structure with assistant of polydopamine (PDA). Hollow metal-PDA particles inherit the shape of MOFs and their metal ions, meanwhile, the shell of hollow structure are assembled by coordination of PDA and metal ions (Co2+ and Zn2+). In other words, the hollow structure and introducing heteroatoms into particles are achieved in one step. This hollow metal-PDA complex with well-organized structure can be further transformed into respective porous carbon materials with structure retention after high temperature treatment. The MOFs as templates not only provide morphology but also supply metal ions to coordinate with PDA forming metal-PDA shell structure due to MOFs’ decomposition. PDA self-polymerized from dopamine, well known for its strong chelating capability with many kinds of metal ions, works as N-doping carbon source. At the meantime, metal ions can be evenly dispersed into porous hollow carbon structure because metal ions coordinate with PDA. After the carbonization, highly homogenous dispersed metal-N-C active sites render the carbon material with high surface area a superior catalyst for ORR in alkaline solution. We believe that this work endows a new strategy for designing and synthesizing hollow metal-organic nanoparticles with diverse morphologies which may have potential applications in various fields.

126

Metal-Support Interaction of Nobel Metal Catalysts On N-Doped Carbon Nanotubes

Ning, XM1,2, Li, YH1, Dong, BQ1, Wang HJ1, Yu, H1, Peng, F1


1 South China University of Technology, Guangzhou, China 2 Lingnan Normal University, Zhanjiang, China

Nitrogen-doped carbon nanotubes (NCNTs) have been widely acknowledged as new-generation supporting materials for noble metal catalysts because of the unique metal-support interaction (MSI). In this contribution, we present the fundamental understanding of the MSI of Pt and Pd nanoparticles (NPs) on NCNTs. Density Functional Theory calculations show that graphitic nitrogen (NG) behaves as an electron donor, while pyridinic nitrogen (NP) as an acceptor of electrons, as a noble metal atom is anchored nearby. The MSI on N sites can be experimentally revealed by the mutual shifting of binding energies of N1s and metal core level XPS signals. We demonstrated that the anchoring sites of metal NPs could be controlled by optimizing the metal loading and synthetic strategy. Pt NPs are preferentially interacted with NG in ethylene glycol (EG) reduction method due to the electron donating property of NG, while preferentially interacted with NP and defects in the impregnation-H2-reduction method due to the vacancies containing NP favouring the metal ion adsorption. In addition, NP sites strongly interact with Pd NPs prepared by the NaBH4 reduction method. Catalytic tests show that the electron enrichment of Pt on NG improves the activity in the electro-oxidation of glycerol, formic acid and CO. Electron-deficient Pt NPs are more active in ammonia borane hydrolysis. The activity of Pd/NCNTs in the industrial relevant nitrobenzene hydrogenation could be maximized by anchoring Pd on NP sites. It is clear that totally different synthesis should be applied to maximize the activities of reactions benefited from electron-riched or electron-deficient catalysts.

127

Metal-Tannin Coordination Derived Metal/N-doped Carbon Composites for Oxygen Electrocatalysis

Wei, J1, Wang, H. T.2

[email protected] mailto:[email protected]

1School of Life Science and Technology, Xi'an Jiaotong University, Xi'an, Shaanxi 710049, China

2Department of Chemical Engineering, Monash University, Clayton, Victoria 3800, Australia.

The conversion of biomass to valuable carbon composites as efficient non-precious metal electrocatalysts is attractive for the development of commercially-viable fuel cell technology. Herein, we develop a versatile iron-tannin framework ink coating strategy to fabricate cellulose-derived Fe3C/Fe-N-C catalysts using commercial filter paper, tissue or cotton as a carbon source, iron-tannin framework as an iron source, and dicyandiamide as a nitrogen source.[1] Such Fe3C/Fe-N-C composites reveal efficient performance for oxygen reduction reaction in alkaline condition. Furthermore, we synthesize a cobalt (or iron)-polyphenol coordination with crystalline framework for the first time.[2] The crystalline framework is formed driven by the assembly of metal ions and polyphenol followed by self-oxidation polymerization of the organic ligands (polyphenol) themselves during hydrothermal treatment in alkaline condition. The metal (Co or Fe)-polyphenol coordination is further demonstrated to be a renewable source for the fabrication of metal/carbon composites as a nonprecious metal catalyst, which show high catalytic performance for both oxygen reduction reaction and oxygen evolution reaction. Such excellent performance makes metal-tannin coordination to be an efficient precursor to fabricate low-cost catalysts for the large-scale application of fuel cells. Reference [1] J. Wei & H. Wang, Angew. Chem. Int. Ed. 2016, 55, 1355. [2] J. Wei & H. Wang, Angew. Chem. Int. Ed. 2016, 55, 12470.

128

Microperoxidase-11 Adsorption on Graphene: Insights from Molecular Dynamics Simulations

Mijajlovic, M1, Sun, Y2, Penna, MJ3, Valizadeh Kiamahelleh, M2, Yang, W4, Biggs MJ5


Affiliations (Arial, 12 font Italics, Organisation, City, Country) e.g. 1 Newcastle University, Newcastle Upon Tyne, United Kingdom

2 University of Adelaide, Adelaide, Australia

3 RMIT University, Melbourne, Australia

4 Deakin University, Melbourne, Australia

5 Loughborough University, Loughborough, United Kingdom

Microperoxidase-11 (MP11) is a heme-containing peptide with catalytic activities that facilitate oxidation reactions with peroxides. The accompanying electron transfer from the heme group to a solid substrate has allowed utilisation of the reaction in devices ranging from fuel cells to biosensors. Various solid substrates for MP11 adsorption have been investigated in an effort to increase the efficiency or sensitivity of these devices. Among these, carbon-based materials have achieved particular attention. Whereas experimental work has provided evidence of improved performance promoted by carbonaceous substrates, molecular mechanisms by which this is achieved are still elusive, which hampers further improvement by design of novel MP11 adsorbing materials. We have addressed this problem by performing a series of molecular dynamics simulations of MP11 adsorption at a water/graphene interface. By analysing an ensemble of conformations recorded during these simulations, we observe that most of them belong to a limited number of clusters. In agreement with experimental findings, the dominant clusters are characterised with a favourable orientation of the heme group that allows an efficient electron transfer to graphene substrate. Our results, however, also indicate that a non-negligible number of recorded structures are adsorbed in an unfavourable orientation. These results and the methodology by which they have been obtained offer a basis for developing strategies for increasing the efficiency of electron transfer between MP11 and carbon substrates; for example, they allow the identification of surface functionalisations and mutations of the peptide that will boost the fraction of favourable heme group orientations relative to the carbon surface.

129

Microstructural Analysis of Carbonized Wood for CO2 Capture

Hata, T1, Honma S2, Onishi Y3, Ide I3, Bonnamy, S4, Bronsveld, P5

[email protected]

1 Kyoto University, Kyoto, Japan 2 Hokkaido Research Organization, Hokkaido, Japan

3 Lignyte Co. Ltd., Osaka, Japan 4 UMR 7374 - CNRS /Université d’Orléans, Orléans, France

5 University of Groningen, Groningen, The Netherlands

In view of global warming, the adsorption and separation of CO2 gas are necessary to prevent the further increase of its concentration in the atmosphere. The use of fossil fuels has increased in recent times, and there is a growing interest in developing CO2 gas adsorption materials for applications not only in industries but also in offices and homes. The development of a retention method for the low-cost and effective adsorption of CO2 is urgently required. CO2 gas can more easily access micropores dominant in carbonized wood. The authors reported that onion-like carbon structures grow on wood during conventional carbonization. The carbonization of such a material may provide better access for CO2 gas to these micropores. Solid adsorbents from wood were developed at a low cost, in comparison with conventional products, for effective CO2 gas adsorption. The highest CO2 adsorption (5.6 mmol/g at 100 kPa) was achieved for the wood samples with a Fe2+ complex pre-carbonized at 300ºC. In this study high-resolution transmission electron microscopy (HRTEM) and SAXS were used to analyze the micropores, microstructure, and texture to understand the adsorption mechanism. The analytical results by SAXS quantitatively showed the pore distribution in both microstructures and onion-like particles. CO2 adsorption by carbonized wood was found to be influenced by the microstructure due to multigraphene layers and the pores formed by onion-like particles.

130

Microstructural Characterizations of Carbon Fiber on the Nanometer Scale

Guo, X.S., Cheng, Y.X., Zhou, G.H., He, L.L.


Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Science, Shenyang, China

Carbon fibers (CF) are the important materials which have wide applications in aerospace, sport tools and other industrial fields. It is well known that a structural inhomogeneity, such as nanoporous, a core-skin structure in PAN-based CF is sometimes an inevitable defect which has a significant influence on mechanical properties. However, the details of the core-skin structure was less understood on the nanometer scale. Recently, we developed a new method which can identified structural texture (inhomogeneity) of the CB by using TEM. By using this new characterization method, in addition to revealing the nature of the core-skin structure of T700 CB, A transition region, which is characterised as a high ordered pyrolytic carbon (highly graphited), has been first identified the between the core and skin zone. Moreover, the typical structural differences between the high-strength CF and high-modulus CF and between the Pan-made CF and Pitch-made CF were also identified on the nanometer scale.

Carbon Fibre and related composite materials

131

Rare Earth CeCl3 As Catalyst Filler to Modify the Microstructure and Mechanical Properties of Carbon/Carbon Composites

Deng Hailaing1, Li Kezhi2, Cui Hong1


1 Xi’an Aerospace Composites Research Institute, Xi’an, PR China 2 State Key Laboratory of Solidification Processing, Northwestern Polytechnical University,

Xi’an, PR China

Carbon/carbon composites with density of 1.70-1.75 g/cm3 were produced by chemical vapor infiltration at 1000 ºC using methane and CeCl3 as precursor and catalyst filler, respectively. The catalytic effects on the pyrocarbon (PyC) deposition rate, microstructure and mechanical properties were studied. Results show that PyC deposition rate is accelerated by the present catalyst. The mechanical strength tends to increase before a decrease with increasing catalyst content from 0 to 10 wt% incorporated in the preforms. The flexural and shear strengths exhibit maxima about 335.2 MPa at 5 wt% and 38.8 MPa at 2 wt% catalyst content, respectively. The matrix deposited without catalyst is dominated by alternate layers of smooth laminar/rough laminar (SL/RL) PyCs, while SL/RL/SL PyC matrix is formed at a catalyst content of 2-7 wt%. The catalytic pyrolysis of methane leads to a decrease of the SL layer and formation of nanofilamentous carbon (NFC). The catalyst fillers are encapsulated by PyC at 10 wt% catalyst, inducing the formation of ISO/SL PyC matrix. The flexural and shear strengths are improved by 9.1-44.2 % and 7.8-40.6 %, respectively, compared to the values obtained without catalyst. The reason is the reinforcing effect of NFCs and deflection of cracks on CeC2 fillers. The toughness of the composites is increased after the treatment at 2250 ºC, but the flexural and shear strengths decrease. Relatively high flexural and shear strength retention ratios are achieved at 5 wt% catalyst, whose corresponding values are about 80.6 % and 76.7 %, respectively.

132

Mobile Carbon Dioxide Removal From Vehicles Using Solid Adsorption

Reynolds, C1, Lastoskie, C1, Brusstar, M2

Presenting author’s e-mail: [email protected] 1University of Michigan, Ann Arbor, Michigan, USA

2U.S. Environmental Protection Agency, Ann Arbor, Michigan, USA

Carbon emissions reduction strategies have historically focused on reducing fuel consumption or carbon content, with regulations primarily targeting the light duty sector. Worldwide, 19% of all anthropogenic greenhouse gas emissions come from on-road vehicles. Half of these vehicles are heavy-duty (HD) trucks and buses, but their emissions are largely overlooked in mitigation efforts.

This research project examines the feasibility of Mobile Carbon Dioxide Removal (MCDR) from HD vehicles using porous solid materials, where the exhaust CO2 is adsorbed within the compound structure instead of being emitted to the atmosphere. Then, at regular intervals, heat is used to regenerate the adsorbent bed and siphon off the captured CO2.

Various activated carbons, zeolites, and metal organic frameworks were examined for uptake capacity, water tolerance, and CO2 selectivity. Testing at the EPA’s National Vehicle and Fuel Emissions Lab uses representative wet and dry exhaust to evaluate real-world performance of these materials in the presence of N2, H2O, CO, and NOx. The results indicate that either a full-regeneration but high-cost compound or a low-cost but mediocre-performing compound could accomplish a 30-80% reduction in CO2 emissions from HD vehicles, depending on the infrastructure.

Several MCDR scenarios were compared for CO2 abatement costs: truck or pipeline transport options for light and heavy duty vehicles, stationary capture from a coal power plant, and direct air capture. The results show that an inexpensive but moderately well-performing adsorbent, like BPL activated carbon, can achieve significant emissions reductions at a cost less than half of direct air capture estimates.

133

Modified Carbon Nanofiber Films as Interlayers for Lithium Sulfur Batteries

Gemeng Liang, Xianying Qin, Qing Li, Ming Liu, Baohua Li*, Feiyu Kang


Graduate School at Shenzhen, Tsinghua University, Shenzhen 518055, China

Lithium sulfur battery has been regarded as one of the most promising candidates for next generation energy storage devices. However, the inferior conductivity of sulfur, volume change during the cycling process and the shuttle effect of the dissolved polysulfides restricted its further application. Different kinds of interlayers have been designed and developed to improve the battery performance. In this work, carbon nanofiber (CNF) based interlayers decorated with various functional materials like V2O5, TiO2, cyclized-polyacrylonitrile were fabricated. These interlayers were placed between cathode and separator, hosting as the second current collector as well. Lithium-sulfur batteries with these multifunctional interlayers showed excellent cycling performance due to the strong chemical adsorption between polysulfides and functional components coated on the CNFs. The captured polysulfides could be reused in the next cycle as a result of fast electronic and ionic transfer in the conductive CNF network. Moreover, it was also found that these functional interlayers could suppress the self-discharge of the Li-S batteries at the same time, making it possible to shelve the lithium sulfur batteries for a long time.

134

Modified Chemical Activation of Lignocellulosic Biomass Derived Carbons for Supercapacitors

Pavlenko, V1,2, Abbas Q3, Prikhodko N1,4, Biisenbayev M1, Tuleibayeva S1,

Béguin F3, Mansurov Z1,2



2 Al-Farabi Kazakh National University, Almaty, Kazakhstan 3 Poznan University of Technology, Poznan, Poland

4 Almaty University of Energetics and Communications, Almaty, Kazakhstan

The production of high-quality activated carbons from lignocellulosic biomass for application in advanced energy storage systems in particular the electrochemical capacitors is of great commercial interest because of their high specific surface area, electrical conductivity, electrochemical stability and notably low cost. During this presentation the synthesis and application of microporous carbons derived by improved chemical activation of pre-carbonized rice husk conducted in the medium of an inert atmosphere as well as in a vacuum will be presented. The carbons derived from the rice husk are characterized by high specific surface area of 2400 m2 g-1 (calculated by the method of Brunauer–Emmett–Teller) and total pore volume of 1.05 cm3 g-1 that consisted of 87% micropores with average size of 0.89 nm. Activated carbons were implemented as the active materials for symmetric composite electrodes of electrical double layer capacitors in 1 mol L-1 Li2SO4. Electrochemical investigations performed by cyclic voltammetry, galvanostatic charge-discharge with potential limitations and impedance spectroscopy revealed high performance of carbon materials derived through modified chemical activation procedure especially under aging tests during floating voltage of 1.6 V. In particular the resulting carbons posses a much higher capacitance of 190-200 F g-1 (at 0.2 A g-1) that is much higher than most of available commercial blends of activated carbons e.g., the Norit DLC Supra 30 which in similar conditions possessed 108 F g-1. The effect of porous structure, composition of carbons and their post-treatment conducted after initial chemical activation on the electrochemical performance of supercapacitors will be discussed.

135

Molecular Clustering and Microscopic Dynamics of Water in Ultramicroporous Carbon

Contescu, C. I1, Bahadur, J.2, Mamontov, E.1, and Gallego, N. C.1,


1 Oak National Laboratory, Oak Ridge, Tennessee, USA

2 Bhabha Atomic Research Center, Mumbai, India

Even when not intentionally functionalized, most activated carbon materials have hydrophilic properties and readily adsorb water from the ambient atmosphere. The presence of water in carbon porosity may adversely impact activated carbon’s efficiency as an adsorbent material in humid environments. Water being a polar molecule, its adsorption mechanism on carbons is determined by the balance between fluid-fluid and fluid-solid interactions which are essentially dominated by the hydrogen bonding properties of H2O molecules between themselves and with oxygen-containing groups on carbon. The clustering and dynamics properties of water in the same ultramicroporous carbon (UMC) were investigated in a concerted study using quasielastic neutron scattering (QENS) and small angle neutron scattering (SANS) methods. SANS experiments confirmed that the initial adsorption on as-received carbon is a slow process that goes through formation and multiplication of constant size (8-9 Å) water clusters attached to carbon functional groups. When these groups were removed, there was no significant adsorption at 50 % relative humidity (RH). The QENS experiments were carried out to investigate the dynamics of water molecules in carbons equilibrated to various RH levels. Water in ultramicropores (< 7 Å) appeared immobile, but water in supermicropores (7-20 Å) exhibits rich dynamics, depending on the hydration level. This hydration water does not freeze down to 220 K and does not fill the pores completely, supporting the observations made in the SANS study. These two studies emphasize that the microscopic dynamics of hydration water should always be considered as a factor influencing the other guest molecules in various applications of porous carbon adsorbents. The work at neutron scattering facilities (SNS and HFIR) at Oak Ridge National Laboratory (ORNL) was supported by the Scientific User Facility Division, Office of Basic Energy Sciences, U. S. Department of Energy and by the Laboratory Directed Research and Development program at ORNL. CIC and NCG acknowledge partial support from the Materials Science and Engineering Division, Office of Basic Energy Science, U. S. Department of Energy. JB received support from the Postdoctoral Program at ORNL.

136

Molecular Detection in Liquid by Graphene Hall Measurement

Zhan, H1, Cervenka, J2, Prawer, S1, Garrett, D1


Affiliations (Arial, 12 font Italics, Organisation, City, Country) e.g. 1 School of Physics, The University of Melbourne, Victoria, Australia

2 Institute of Physics ASCR, v.v.i., Cukrovarnicka 10/122, Praha 6, Czech Republic

This work presents a very sensitive technique to detect molecules in low concentration solution by introducing the method of liquid gated Hall measurement. L-Histidine of different concentration in pM range and urea in μM range are measured separately. The results show very good sensitivity in both solutions, while the conventional amperometric and potentiometric techniques do not show satisfactory responses. The possible detection mechanism includes charged impurity scattering, chemical doping, dielectric screening processes, and so on. The ability of measuring very low concentration electrolyte using this method definitely provides a promising future for both experimental and theoretical study of applying this method in bio-sensing.

137

Molybdenum carbide - graphite composites with high thermo-mechanical performance

Guardia-Valenzuela, J1,2, Bertarelli, A1, Carra, F1,3, Mariani, N4

Presenting author’s e-mail: [email protected] 1 CERN, Geneva, Switzerland

2 University of Zaragoza, Spain 3 Politecnico di Torino, Italy

4 ITER, France Recent years show an increase of the industrial demand for ceramic-matrix materials with high thermal conductivity and thermal-shock resistance, in particular in aerospace, friction braking and nuclear sectors. Such materials are usually carbon-based, typically carbon fibre – carbon (CFC). A family of novel graphite-based composites reinforced with a dispersion of molybdenum carbide particles has been recently developed at CERN for applications to particle accelerators. In particular, these materials are suitable for components close to the particle beam, which are submitted to relevant thermal energy deposition, with the consequent rapid increase in temperature and generation of thermal stresses. The composites, produced by rapid hot pressing, have been extensively investigated and characterized. The present paper reports the results of the characterization, as well as the investigation of the influence of parameters such as the initial constituents, the sintering variables and the post-sintering treatments. Analyses of the carbide phases and microstructures are showed and discussed. These composites, featuring an excellent thermal conductivity (740 Wm-1K-1), low thermal expansion and low density, represent an optimal solution for high-end thermal management applications.

138

Monolithic Carbon Electrodes with Ordered Mesopores for High-Voltage Aqueous Supercapacitors

Hasegawa, G1, Kanamori, K2, Nakanishi, K2, Hayashi, K1


1 Kyushu University, Fukuoka, Japan 2 Kyoto University, Kyoto, Japan

A large number of studies in the past few decades have demonstrated the importance of

material design and established an outstanding process to tailor various ordered mesoporous structures, i.e. supramolecular self-organization. Nowadays, however, the increasing demand for nanostructured materials poses more stringent requirement; the structural design over broad length scales, which needs more complicated and costly process, is required for a practical use.

In this study, we have developed a facile one-pot synthesis of macroporous polymer scaffolds comprising mesoporous nanorods with two-dimensional (2-D) hexagonal ordering by combining the micellar templating in nanometer-scale with the phase separation in micrometer-scale. The tailored multilevel pore system in the polymer scaffolds can be preserved through carbonization and thermal activation, yielding the multimodal porous carbon and activated carbon (AC) monoliths. The thin columnar macroframeworks are beneficial for electrode materials due to the short mass diffusion length through small pores (micro- and mesopores).

We have also explored the capability of “water-in-salt” electrolytes, aiming at high-voltage aqueous supercapacitors by employing the nanostructured AC monolith as a binder-free electrode. Despite the formation of salt-derived decomposition products on electrode surface, the effective surface area contributing to electric double-layer capacitance in 5 M bis(trifluoromethane sulfonyl)imide (LiTFSI) is found to be comparable to that in a conventional neutral aqueous electrolyte. The expanded stability potential window of the superconcentrated electrolyte allows for a 2.4 V-class aqueous AC/AC symmetric supercapacitor with good cycle performance.

139

Multifunctional carbon-based metal-free catalysts for efficient energy conversion and storage

Chuangang Hu and Liming Dai Case Western Reserve University, USA

Renewable energy technologies, such as fuel cells, batteries, and water-splitting, hold

promise to solve current energy and environmental challenges. However, noble metal catalysts are needed to promote the hydrogen evolution reaction (HER) for hydrogen fuel generation from water-splitting, oxygen reduction reaction (ORR) in fuel cells for energy conversion, and oxygen evolution reaction (OER) in metal-air batteries for energy storage. The high cost of precious metals and their limited reserve have precluded these renewable energy technologies from large-scale applications.

We have demonstrated that nitrogen-doped carbon nanotubes could be used to replace Pt for catalyzing ORR in fuel cells with an excellent activity and long-term durability. This is because the doping-induced charge transfer can change the chemisorption mode of O2 to facilitate the ORR. Furthermore, various carbon nanomaterials doped with one or more heteroatoms, physically adsorbed with certain polyelectrolytes, and contained some defects, could also exhibit good ORR performance caused by polyelectrolyte or defect-induced charge redistribution. Recently, it was found that heteroatom-doped _ENREF_8carbon nanomaterials can even act as metal-free ORR and OER or HER bifunctional catalysts for water-splitting to generate H2/O2 gases, metal-air batteries for energy storage, and even ORR/OER/HER trifunctional catalysis for integrated energy systems.

In this talk, we will summarize some of our work on the metal-free catalysts based on carbon nanomaterials for various energy-related reactions, along with an overview on the recent developments and perspectives in this exciting field.

140

Multifunctional graphene membrane for lithium sulfur batteries

Huang, JQ1,2, Zhuang, T2, Peng, HJ2, Zhang, Q2


1 Advanced Research Institute for Multidisciplinary Science, Beijing Institute of Technology, Beijing 100081, China

2 Beijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing 100084, China.

Lithium sulfur batteries attract great attention due to their high energy density, while

the real applications are still hindered by the rapid capacity degradation. Despite great effort devoted to solving the polysulfide shuttle between the cathode and anode electrodes, it remains as a serious challenge to build high-stable lithium sulfur battery, which related to the diffusion and reaction between polysulfides and the metal lithium anode.

We proposed a strategy of introducing an ion selective membrane to improve the stability and coulombic efficiency of lithium sulfur battery. With the permselective membrane, the polysulfide anions can be confined in the cathode side, which would favor the cyclic stability and lower self-discharge performance.

A unique lithium-sulfur battery configuration with ultrathin graphene oxide (GO) membrane for high stability. The oxygen electronegative atoms modified GO into a polar plane and the carboxyl groups acted as ion hopping sites of positively charged species (Li+) while rejected the transportation of negatively charged species (polysulfide anions) due to the electrostatic interactions. Such electrostatic repulsion and physical inhibition largely decreased the transference of polysulfides across the GO membrane in lithium-sulfur system. By the incorporation of permselective GO membrane, cyclic capacity decay rate is also reduced from 0.49 to 0.23 %/cycle. With GO membrane, the lithium sulfur batteries also exhibit an improved Coulombic efficiency from 67-75% to over 95-98% at 0.1 C.

Such ion selective membrane is versatile for various electrodes and working conditions, which is promising for the construction of high performance batteries. [1] Huang, J. Q.; Zhuang, T. Z.; Zhang, Q.; Peng, H. J.; Chen, C. M.; Wei, F.

Permselective Graphene Oxide Membrane for Highly Stable and Anti-Self-Discharge Lithium-Sulfur Batteries. ACS Nano 2015, 9, 3002-3011.

141

Nanocarbon and nanocarbon supported metal catalysts for Light Alkanes Activation

Yajie Zhang, Jia Wang, Jiangyong Diao, Dangsheng Su and Hongyang Liu


Shenyang National Lab for Material Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang, 110016, China

Nanocarbon is a term increasingly used to indicate the broad range of carbon materials having a tailored nanoscale dimension and functional properties that significantly depend on their nanoscale features. Recently, lots of studies have demonstrated that nanocarbons, such as carbon nanotube (CNT), porous graphene and nanodiamond (ND) can be used as metal free catalysts for the light alkanes dehydrogenation reactions, showing their potential applications to replace the traditional metal oxide catalysts. In this report, we will not only present our recent studies about the exploration of nanocarbons as metal free catalysts for the industrial dehydrogenation reactions, but also we will introduce the fabrication of nanocarbon materials (carbon nanotube, hollow carbon sphere and hollow graphene nanoshell) embedded by Au and Pd NPs used in catalytic oxidation and hydrogenation reactions, and the stabilization of Pd and Pt NPs on novel nanodiamond–graphene with core–shell supports for light alkanes dehydrogenation. The detailed preparing process, characterization, catalytic performance and mechanism will be carefully discussed in the report [1-2].

Keywords: Nanocarbon; Supported metal; Graphene; Confinement References: 1. H.Y. Liu, L.Y. Zhang, N. Wang, D. S. Su, Angewandte Chemie International Edition, 2014, 53(46), 1263; L.Y. Zhang, H.Y. Liu, Z. Jiang, D.S. Su, Angewandte Chemie International Edition, 2015, 54(52), 15823. 2. H.Y. Liu, J. Wang, D.S. Su, Small, 2015, 11(38), 5059; J.Y. Diao, R. Huang, H.Y. Liu and D.S. Su, ChemSusChem. 2016, 9, 662; X. R. Zhang, Z.S. Meng, H.Y. Liu and R.F. Lu, Energy & Environmental Science, 2016, 9(3), 841.

142

Nanocarbons for electrochemical energy storage

Hui-Ming Cheng1,2

1Shenyang National Laboratory for Materials Science Institute of Metal Research, Chinese Academy of Sciences

72 Wenhua Road, Shenyang 110016, China

2Laboratory for Low-Dimensional Materials and Devices

Tsinghua-Berkeley Shenzhen Institute (TBSI), Tsinghua University

1001 Xueyuan Road, Shenzhen 518055, China


Keywords: Nanocarbons, Battery, Supercapacitor, Carbon nanotubes, Graphene

In recent years, electrochemical energy storage devices, such as supercapacitors, lithium-ion batteries and lithium-sulfur batteries, have been extensively explored in response to the ever-increasing demand for clean energy and climate change mitigation technologies. Carbon materials with different structures and functionalities play a key role in various energy storage devices for use as electrodes, conductive fillers, coating layers, etc. Nanocarbons, including carbon nanotubes (CNTs) and graphene have unique low-dimensional structures, good electrical conductivity, high strength, and desirable chemical stability. Therefore, nanocarbons are expected to find extensive and important applications in the field of electrochemical energy storage.

We have fabricated a serious of nanocarbon-based hybrid electrode materials by mechanical mixing, hydrothermal deposition, in-situ growth, or selective filling. These hybrid electrode materials showed desirable electrochemical properties in terms of long cycling life, good high rate capability, and high reversible capacity. The working mechanism of nanocarbons in hybrid electrodes was investigated by an in situ TEM approach. It was found that nanocarbons take a significant role in forming electrical conductive network and preventing the volume expansion of active materials. And we also designed and developed nanocarbon-based sandwich structure, integrated structure and flexible structure for high-capacity, high-power, long-life and high energy lithium-sulfur batteries.

Using graphene and CNTs in flexible energy storage devices is another emerging field, and we have also explored several kinds of nanocarbon-based flexible electrodes. Based on the understanding of electric double layer and tuning electrochemical potential windows, a smart lithium ion capacitor with an extra Li electrode to monitor the operation state and to regenerate its capacity was developed, which can allow a real-time diagnosis of capacity decay, safety control, and self-healing of a degraded capacitor through a feedback system. The smart electrochemical energy storage devices can work as a bridge that connects users and R&D engineers to create a safer and more intelligent electrochemical energy storage future.

143

Nanocarbons in novel solar cells

Yu, L., Batmunkh, M., Dadkhah, M., Shearer, C. J., Tune, D. and Shapter, J. G.


School of Chemical and Physical Sciences, Sturt Road, Bedford Park, South Australia, 5042, Australia

One of the most important issues facing society is the ability to supply the world’s energy requirements via both environmentally responsible and sustainable means. Renewable energy, and in particular solar energy, has the potential to address current issues in energy production but costs, both in terms of the energy required for production and final price to the consumer, as well flexibility in terms of system deployment are problems that will need to be addressed. This talk will focus on work using carbon nanomaterials to make new architectures for solar cells. Several possible structures will be explored and the disadvantages and advantages of each will be examined.

144

Nanostructure Control of Graphenes for Highly Efficient and Stretchable Supercapacitors

Jeong Gon Son

[email protected]

Korea Institute of Science & Technology, Seoul, South Korea

Graphene has great interests because of its incredible properties for the potential future applications, such as high electrical & thermal conductivity, high surface area and their transparency, from molecular-levelly thin two-dimensional materials. In this talk, we fabricated three-dimensional (3D) graphene structures with templated-

assisted crumpled graphene approach and directionally porous ice-templated approach for the energy storage application, such as supercapacitor electrodes. We introduce a sea urchin-like spiky template with simultaneous chemical etching/reduction process for the fabrication of 3D crumpled graphene balls. And, using a facile ice-templated self-assembly process with reduced graphene sheets and vanadium phosphate (VOPO4) nanosheets, we realize a three-dimensional (3D) porous graphene/VOPO4 nanosheet nanocomposite with high surface area and high electrical conductivity for the enhanced pseudocapacitive properties. In the last part, we also used the ice-templated vertically porous graphene nanostructures

as a stretchable supercapacitor electrode. Radially compressed honeycomb structures exhibited nearly-zero poission ratio structures and maintained their structure and electrical conductivity even at 50 % of starched states. The capacitive performance of these compressed honeycomb structures also shows fairly high over 130 F/g and these high performance still be maintained at highly stretched condition.

145

Nanostructured Graphene to Inhibit Li-Dendrite Growth in Safe Li-Metal Batteries

Xin-Bing Cheng1, Hong-Jie Peng1, Jia-Qi Huang1, Rui Zhang1, Chen-Zi Zhao1, Qiang Zhang1,*


1 Department of Chemical Engineering, Tsinghua University, Beijing 100084, China

Li metal is considered as the “Holy Grail” of energy storage systems. The bright prospects give rise to worldwide interests in the metallic Li for the next generation energy storage systems, including highly considered rechargeable metallic Li batteries such as Li-O2 and Li-sulfur (Li–S) batteries. However, the formation of Li dendrites induced by inhomogeneous distribution of current density on the Li metal anode and the concentration gradient of Li ions at the electrolyte/electrode interface is a crucial issue that hinders the practical demonstration of high-energy-density metallic Li batteries.

Free-standing graphene foam provides several promising features as underneath layer for Li anode, including (1) relative larger surface area than 2D substrates to lower the real specific surface current density and the possibility of dendrite growth, (2) interconnected framework to support and recycle dead Li, and (3) good flexibility to sustain the volume fluctuation during repeated incorporation/extraction of Li. The synergy between the LiNO3 and polysulfides provides the feasibility to the formation of robust SEI in an ether-based electrolyte. The efficient in-situ formed SEI-coated graphene structure allows stable Li metal anode with the cycling Coulombic efficiency of ∼97 % with high safety and efficiency performance. These results indicated that interfacial engineering of nanostructured electrode were a promising strategy to handle the intrinsic problems of Li metal anodes, thus shed a new light toward LMBs, such as Li-S and Li-O2 batteries with high energy density.

Reference

[1] X. B. Cheng, H. J. Peng, J. Q. Huang, F. Wei, Q. Zhang, Small 2014, 10, 4257 [2] X. B. Cheng, H. J. Peng, J. Q. Huang, R. Zhang, C. Z. Zhao, Q. Zhang, ACS Nano

2015, 9, 6373. [3] R. Zhang, X.B. Cheng, C.Z. Zhao, H.J. Peng, J.L. Shi, J.Q. Huang, J.F. Wang, F. Wei,

Q. Zhang. Adv Mater 2016, 28, 2155. [4] X.B. Cheng, T.Z. Hou, R. Zhang, H.J. Peng, C.Z. Zhao, J.Q. Huang, Q. Zhang, Adv

Mater 2016, 28, 2888. [5] X.Q. Zhang, X.B. Cheng, X. Chen, C. Yan, Q. Zhang, Adv Funct Mater 2017, 27,

1605989

146

N-Doped Carbon Quantum Dots Toward Electroluminescence

Zheng J X1, 2, Ding Y F1, 2, Miao Y Q1, 2, Yang Y Z1,2, Liu X G1,3, Jia H S1

[email protected]; [email protected]

1 Key Laboratory of Interface Science and Engineering in Advanced Materials, Ministry of Education, Taiyuan 030024, China

2 Research Center of Advanced Materials Science and Technology, Taiyuan University of Technology, Taiyuan 030024, China

3 College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, China

N-doped carbon quantum dots (N-CQDs) were synthesized through one-step hydrothermal method using phthalic acid as carbon source and ethylenediamine as additive. The as-prepared N-CQDs have a fluorescent quantum yield of 29.3% and exhibit excitation-dependent property with altering excitation wavelength. Transmission electron microscopy, atomic force microscope, Fourier transform infrared spectrometry and X-ray photoelectron spectroscopy were employed to investigate the morphology and structure of the N-CQDs. The highest occupied molecular orbital and lowest unoccupied molecular orbital energy levels of N-CQDs were calculated to be -7.28 eV and -4.09 eV, respectively, by electrochemical method. Solution-processed electroluminescent light-emitting diodes (LED) was fabricated using N-CQDs as emitting layer based on the device structure of ITO /poly(ethylenedioxythiophene):polystyrene sulfonate/N-CQDs/1,3,5-tris(N-phenylbenzimidazol-2-yl) benzene/LiF-Al. The effects of N-CQDs dosage and the speed and time of spin-coating on optical performance of LED device were investigated. The results indicate that N-CQDs, with the size of 4-7 nm, have crystalline structure with lattice spacing of 0.22 nm corresponding to the (100) facet of graphite. The film of N-CQDs has good smoothness and density. When the N-CQDs dosage and the speed and time of spin-coating are 360 μL, 1000 rpm and 30 s, respectively, the device emits blue light with a luminance of 4.9 cd/m2 and a turn-on voltage of 5.5 V.

147

N-Doped Mesoporous Carbons Decorated with PT Nanoparticles in Hydrotreatment Reactions

Ruiz-García C, F. Heras, N. Alonso-Morales, L. Calvo, J.J. Rodriguez, M.A. Gilarranz

[email protected]

1 Aplicada Sección de Ingeniería Química, Universidad Autónoma de Madrid, Madrid, Spain

New carbon materials, such as doped carbons have been studied in the last years with the focus in the development of different applications, such as electrochemical devices (batteries and supercapacitors), CO2 and H2 sorbents, sensors or catalysts. The insertion a doping atom in the carbon matrix modifies chemical and electronic properties, giving an improved performance. It is also well know that materials with a specific morphology can be prepared using a template strategy. By combining these two approached, it is possible to obtain tailored porous and doped carbons. The objective of this work is to prepare N-doped mesoporous carbons and use them as support of Pt nanoparticles to study the influence of N-doping in the activity of the catalysts in liquid phase hydrodechlorination. Carbons were prepared by infiltration of resol resin (carbonaceous precursor) and 1,10-phenantroline (N-doping agent) in a SBA-15 (mesoporous silica template). The infiltrated template was pyrolyzed at 700ºC, and then the template was removed. Pt nanoparticles were prepared by colloidal synthesis using H2PtCl6 as Pt precursor, polyvinylpyrrolidone as capping agent and NaBH4 as reducing agent. PVP was removed after impregnation of the nanoparticles in carbon. Samples were characterized by elemental analysis, X-ray photoelectron spectroscopy, nitrogen adsorption-desorption and electron microscopy. The Pt/C catalysts were checked in the hydrodechlorination of a model compound (4-chlorophenol). Activity and selectivity results showed the difference in the behaviour of the catalyst depending on the presence of dopant atoms.

148

New Carbon Adsorbents for CO2 Capture and Separation

Martin-Calvo, A1, Finsy, V2, Baron, G. V1, Dubois, E2, Denayer, J. F. M1


1 Vrije Universiteit Brussel, Brussels, Belgium 2 Solvay, Brussels, Belgium

In spite of the huge number of new porous materials developed in recent years (zeolites, MOFs, COFs, ZIFs…), the use of carbon based materials for molecular separation purposes remains extremely important for industrial applications as a result of, among others, the unique stability of such materials, their low production cost, and hydrophobic properties. In this work, we have studied the use of novel porous carbon adsorbents for CO2 capture and separation from flue gas. A large series of porous carbon materials was characterized in detail for their adsorption/desorption kinetics, adsorption equilibrium and stability in cyclic processes in presence of poisons (SOx and NOx). With this aim, gas phase breakthrough experiments have been performed using CO2/N2 mixtures with and without impurities. The effect of water has also been studied considering different moisture percentages. Desorption kinetics have been explored using the Zero Length Column (ZLC) method. Due to the nature of the materials, we have found that the main limitation of this technique resides in the Mass Spectrometry detection method. Refining of the method has allowed demonstrating the impact of material optimisation on adsorption and transport properties.

149

New Graphene Templating Methods to Fabricate Complex Metal Oxide Topographies

Liu, M, Chen, P-Y, Hurt, RH

[email protected]

Brown University, Providence, United States

Confined assembly in the intersheet gallery spaces of two-dimensional (2D) materials is an emerging templating route for creation of new material architectures. Graphene oxide (GO) is selected as a freeform nanomold because of high flexibility, tunable interlayer spacing, water processibility and ease of removal by oxidation. Here, we demonstrate and compare two general synthetic routes for transcribing complex topographies from shaped GO structures into metal oxides: 1) Intercalation of hydrated metal ions into pre-textured GO multilayer films followed by dehydration, and air oxidation to produce Zn, Al, Mn, and Cu oxide films with high-fidelity replication of the original GO textures. The textured metal oxides are shown to consist of nanosheet-like aggregates of interconnected particles, whose mobility, attachment, and sintering are guided by the 2D template. 2) Casting of charge-inverted GO-metal ions hybrid nanosheets and their conversion to 2D-patterned or 3D-shaped metal oxides. 2D patterning is achieved by casting GO-Mn+ hybrid onto a pattern to be replicated, while 3D shaping is achieved by forming dry GO-Mn+ papers that can be folded or shaped prior to template removal. Conditions have been found in which the underlying nanostructure of the metal oxide bodies consists of anisotropic platelet crystals perfectly connected and tiled in 2D to form robust, space-filling nanosheets. Potential applications of these graphene-templated metal oxide structures will be discussed, including their use to make metal oxide replicas of surface textures found in nature (on leaves, hair) and arbitrary 3D geometric objects (loops, fibers).

150

Next generation carbon fibres using nano-enhanced PAN precursors Salim, NV, Razal, JM


Deakin University, Geelong, Australia

Carbon fibre composites are materials where carbon fibres are embedded in a polymer matrix. They are increasingly used across a vast range of industries such as aerospace, automotive and oil and gas to replace steel and aluminium. This demand forecasts for the global carbon fibre demand to increase at an annual rate of 13-17 % to 2020. This means that the carbon fibre precursor production also need to increase. To date, around 90% of carbon fibre is derived from polyacrylonitrile (PAN) precursors. It is also predicted that carbon fibres can be made 10 times stronger than the current standard; however this has not been achieved to date because of the limited understanding of the complex nature of the synthesis process. In a pivotal work by Satish Kumar and co-workers, reinforced PAN was achieved by the addition of small amount of carbon nanotubes (CNTs).1 However, in bulk production CNT based fibres lack quality as the poor CNT dispersion creates CF graphitic layers to follow the curvature that leads to imperfections.2 Currently graphene nanoparticles are used as the most important composite reinforcement material due to their low cost and properties that rival those of CNTs.3This presentation details the incorporation of novel liquid crystalline graphene oxide (LCGO) in PAN to induce polymer chain crystallisation and orientation leading to high performance of the carbon fibre precursors. The LCGO dispersions display unique liquid crystallinity in various solvents and more importantly, the LC behaviour enables continuous production of unlimited lengths of novel fibres with excellent mechanical properties and high conductivity.4

References 1Sreekumar, et al. Adv. Mater. 2004,16, 58. 2Maitra et al. Carbon 2012, 50, 1753. 3Xiang et al. Acs Nano, 2013, 7, 1628. 4 Jalili et al. Adv. Funct. Mater. 2013, 23, 5345.

151

Nitrogen doped carbon aerogel - graphene composite materials for electrocatalysis

Nagy, B1, Bertóti, I2, Mohai M2, Bakos, I2, László, K1


1 Budapest University of Technology and Economics, Budapest, Hungary 2 Research Centre for Natural Sciences, Hungarian Academy of Sciences, Budapest,

Hungary

Nitrogen is the most versatile heteroatom in carbon matrices. It affects both the physical and the chemical behaviour of carbons already at low concentration (<1.5%) by influencing the electron distribution and thus the electrical, hydrophilic/hydrophobic and catalytic properties. Nitrogen doped carbon materials have a great potential in energy conversation and storage e.g., as catalyst in the oxygen reduction reaction (ORR) of fuel cells. The electrical conductivity of the carbon materials is crucial in these applications. Incorporation of graphene into the porous carbon matrix can further improve the electrical conductivity without deteriorating their beneficial properties. Sol-gel techniques have been applied to prepare polymer aerogels of tailored structure, which are excellent precursors for porous carbon. Due to the flexibility of this synthesis route heteroatoms or nanoparticles can be easily incorporated into the carbon matrix. In this work nitrogen doped carbon aerogel - graphene composite materials were prepared from resorcinol (R) – melamine (M) – formaldehyde (F) copolymers. Graphene was incorporated as graphene-oxide suspension during the polymerization process. The polymer hydrogels were dried by supercritical CO2 and converted to carbon by heat treatment in inert atmosphere. The morphology of the carbon aerogels obtained was characterized by low temperature nitrogen adsorption/desorption isotherms and scanning electron microscopy (SEM). The surface chemical composition was determined by X-ray photoelectron spectroscopy (XPS). The catalytic performance in ORR was followed by cyclic and linear sweep voltammetry (CV, LSV). Samples prepared without melamine were used for comparison.

152

Nitrogen doped hierarchically porous graphene for high energy density Supercapacitors

Kota, M1, Park, H.S1

[email protected]

1 Sungkyunkwan University, Gyeonggi-do, Republic of Korea

We report synthesis of nitrogen doped three dimensional graphene (N-RGO) architectures. The incorporation of nitrogen into the lattice of graphene is confirmed through transmission electron microscopy analysis and the detailed doping configurations analysed by X-ray photoluminescence spectroscopy indicate the nitrogen content of around 6.2 at.% in the N-RGO with predominant pyridinic N-type configuration. The reduced graphene oxide has specific surface area of 190 m2 g-1 and specific capacitance up to 217 F g-1 at a scan rate of 5 mV s-1.The low charge transfer resistance confirmed by electrochemical impedance spectroscopy is associated with good rate capability. The N-RGO sample exhibits an excellent cyclic stability with no decay in capacitance even after 5000 cycles at scan rate of 100 mV s-1. A further study for high energy density supercapacitor (SC) is conducted by introducing micro porosity and 1-ethylimidazolium tetrafluoroborate (EMIMBF4) ionic liquid (IL) electrolyte in to the system, which is to be discussed.

153

Nitrogen-Doped Porous Carbon Monoliths from Polyacrylonitrile (PAN) and Carbon Nanotubes as Electrodes for Supercapacitors

Yanqing Wang1*, Bunshi Fugetsu1, 2, Zhipeng Wang3, Wei Gong1, Ichiro Sakata1, 2, Shingo

Morimoto3, Yoshio Hashimoto3, Morinobu Endo3, Mildred Dresselhaus4

& Mauricio Terrones5

[email protected]

1School of Engineering, The University of Tokyo, Bunkyo-ku, Tokyo 113-0032, Japan. 2Policy Alternative Research Institute, The University of Tokyo, Bunkyo-ku, Tokyo 113-

0032, Japan. 3Institute of Carbon Science and Technology, Shinshu University; 4-17-1 Wakasato,

Nagano 380-8553, Japan. 4Research Laboratory of Electronics, Department of Electrical Engineering and Computer

Science, Department of Physics, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, MA 02139-4307, USA.

5Department of Physics, Department of Chemistry, Department of Materials Science and Engineering and Center for 2-Dimensional and Layered Materials, The Pennsylvania State

University, University Park, PA 16802, USA. Fabrication of hierarchical porous activated carbon monoliths (ACMs) with high surface area, pore volume, also with controllable morphology and nitrogen-doped functionality has always been pursued. However, the currently effective template methods and Lewis acid/base activation strategy suffer from the drawbacks of either high costs or tedious preparation steps. Herein, 3D ACMs with macro-mesoporous networks and regulative morphologies were facilely fabricated via a template-free two step method from polyacrylonitrile (PAN) and a carbon nanotubes (CNTs) based dispersion solution. The first step is the fabrication of the continuous mesoporous polymeric PAN and PANCNT monoliths by an advanced template-free temperature-induced phase separation (TTPS) technique. The polymeric monoliths have network/non-network structures that can be controlled by combined action of the diffusion of the water phase and the formation of a solid phase in the TTPS process. The next step is the transformation of polymeric monoliths into ACMs by a heat treatment process. During this step, the produced ACMs maintain their original shape and special morphology without drastic volume shrinkage or cracks. The obtained ACMs show a high surface area value up to 613.8 m2/g and a large pore volume (0.366 cm3/g). The developed mesoporous network in 3D is favorable for fast electrolyte ionic transport in the porous carbon channels. The ACMs demonstrated excellent specific capacitance (216 F/g), low equivalent series resistance (ESR), and non-decreased/increased capacitance retention even after 3000 cycles as supercapacitor electrode materials, indicating the efficient diffusion and adsorption of electrolyte ions in the designed hierarchically porous structure.

154

Numerical And Experimental Characterization Of Kerogen Phases Nano-Pore Network

R. J.-M. Pellenq1,2,3, J. Berthonneau2,3, P.-L. Valdenaire2,3, A. Obliger2,3, O. Grauby3, D. Ferry3, J.-M. Leyssale2 and F. Ulm1

[email protected]

1CEE, Massachusetts Institute of Technology, Cambridge MA, United States 2 <MSE>2, the CNRS / MIT / Aix-Marseille Université Joint Laboratory, Massachusetts

Institute of Technology, Cambridge MA, United States 3CINaM, CNRS / Aix-Marseille Université, Campus de Luminy, Marseille, France

The geometry of the organic pore networks plays a key role in controlling the fluid transport properties of source rocks. Its characterization is challenging because a significant portion is comprised between 0.1 and 50 nm in diameter1. This micro to meso-porosity is responsible for the low permeability, strong adsorption, and non-Darcy behaviour of these geomaterials2. It results in reduced hydrocarbons flow, partly accounting for the fast productivity declines noticed in exploitation wells around the globe3. In order to improve the accuracy of production predictions, it is paramount to understand the evolution of organic hosted pores in terms of morphology and topology as a function of thermal maturity. Sub-nanometer pore networks were characterized through Hybrid Reverse Monte-Carlo/MD atomistic simulations. For three different formations (Lower Eagle Ford, Marcellus, and Haynesville) containing variable contents of organic material with different thermal maturities (LEF is thermally immature and oil-prone whereas MAR and HAY are thermally overmature and gas-prone)4, we show that kerogen phases exhibit a sub-nanometer porosity whose degree of connectivity relates to the level of maturity. As the scale immediately above, an experimental study was therefore initiated by coupling BET with electron tomography using FIB thin sections. The analysis of 3D reconstructed images showed that the pore size distributions and surface areas from aperture map computations, chord length distributions, and surface meshing are in good agreement with the N2 adsorption isotherms. Again, depending on seems the degree of maturity, striking changes in pore connectivity and size distribution are observed. Altogether, these results combining two different length scales constitute a major discovery impacting directly field production and allow setting-up useful and realistic multiscale models to study hydrocarbon molecules transport properties. [1] Clarkson, C. et al (2013), Fuel, 103, pp. 606-616 [2] Falk K. et al (2015), Nature Communications, DOI: 10.1038/ncomms7949 [3] Patzek T. et al (2013), PNAS, 110, pp. 19731-19736 [4] Bousige C. et al (2016), Nature Materials, DOI: 10.1038/NMAT4541 [5] Valenza J. et al (2013), Geology, DOI: 10.1130/G33639.1

155

Direct observation of graphene destruction and reconstruction by in situ TEM

Yichun Yin1, Xun Zhang2, Yong Wang2, Chenghua Sun3

[email protected]

1School of Chemistry, Monash University, Clayton, VIC 3800, Australia 2Center of Electron Microscopy and State Key Laboratory of Silicon Materials, School of

Materials Science and Engineering, Zhejiang University, Hangzhou 310027, China 1,3Department of Chemistry and Biotechnology, Faculty of Science, Engineering and

Technology, Swinburne University of Technology, Hawthorn, VIC 3122, Australia

Defective graphene with additional density of states offers versatile possibilities for catalytic applications. Controlling formation of defects and exploring the mechanism are vital. In this work, a molten salt method has been applied to create defects on graphene without aid of reducing atmosphere like hydrogen. Hole defects expanding, tearing and new layer forming have been directly observed by in situ transmission electron microscope (TEM). First principle calculations revealed the destruction and reconstruction are driven by the ions in molten salt. This provides an effective approach for defective graphene and in depth study of defects mechanism.

156

On the Reconciliation of the Commensurate-Incommensurate Transition between Experimental Data and Computer Simulation for Krypton Adsorption on Graphite

Tan, S1, Prasetyo, L1, Horikawa, T2, Do, D. D1, Nicholson, D1

[email protected]

1 University of Queensland, Brisbane, Australia 2 The University of Tokushima, Tokushima, Japan

The Steele 10-4-3 potential model for graphite is commonly used in the literature to simulate adsorption of gases. However, the simplicity of this model and its inherent assumptions fail to describe many fine features displayed in the experimental adsorption isotherm and the isosteric heat versus loading, especially in the sub-monolayer region. To this end, we propose a new model for graphite that accounts properly for the following energetic and geometric characteristics of graphite: (1) the different energetic behaviour of the uppermost graphene layer from the layers underneath, (2) the variation of the spacing between layers close to the uppermost layer, (3) the geometric corrugation of the uppermost graphene layer, (4) the anisotropy of carbon atom in a graphene layer, (5) the variation of the anisotropy with surrounding neighbouring molecules, and (6) the smaller collision diameter of carbon atom of the uppermost layer. With these characteristics of the new model for graphite we are able, for the first time in the literature, to describe many features that are displayed in the isotherm and the isosteric heat versus loading, for example the correct transition from liquid-like adsorbate to commensurate solid and the subsequent transition from the commensurate solid to incommensurate solid. Most importantly, we are able to describe the physics of the spike observed experimentally in the isosteric heat curve versus loading, and finally the evolution of the transitions mentioned above and the heat spike with respect to temperature is properly described by the new graphite model.

157

Operando study of carbon electrode degradation mechanisms in environmental-friendly supercapacitors

Frackowiak, E1, Fic, K1, He, M2, Berg, E.J2, Novak, P2


1 Poznan University of Technology, Poznan, Poland 2 Paul Scherrer Institute, Electrochemistry Laboratory, 5232 Villigen PSI, Switzerland

This paper reports on the operando study of activated carbon electrode degradation mechanisms in water-based electrolytes (1 mol L-1 Li2SO4 and LiNO3 solutions).

In order to present more in-depth insight into the interfacial processes, the electrochemical investigations have been supported by on-line electrochemical mass spectrometry (OEMS) and in-situ Raman spectroscopy. The discussion of the results will demonstrate that the electrode performance fade might have a different origin, although the electrochemical response in various electrolytes is similar. Briefly, for capacitor operating with 1 mol LiNO3 solution it has been observed that NO3

- specimen seems to be reactive with a carbon electrode, essentially at high potentials values. Moreover, the oxidation of the electrode by NO3

- appeared to be reversible with incremental capacitance increase. Furthermore, the hydrogen generation on the negative electrode plays a protective role for both electrodes, neutralizing tentatively generated O-based radicals and preserving the electrode surface against oxidation. On the other hand, both in-situ Raman spectroscopy and OEMS techniques proved the evolution of CO2, NO2, and NO gasses.

A detrimental effect of oxygen evolution at elevated voltages (up to 1.8 V) has also been observed. An in-depth study involving the implementation of the operando techniques also allowed the most optimal voltage for both systems to be determined, taking into account their long-term performance as well. Finally, the results obtained proved that similar electrochemical response of the carbon electrodes, essentially in terms of performance fade, may have a various origin and requires a different approach for further development.

158

Orientation of Graphite Layers in Polyacrylonitrile Based Carbon Fibres

Fakhrhoseini, S.M1, Khayyam, H1, Naebe M1


1 Institute for Frontier Materials, Carbon Nexus, Deakin University, Victoria 3216, Australia

Physical properties of carbon fibre are strongly related to the axial orientation of graphite layers. Conventionally, stretching stabilised fibres in carbonisation step and carbonising at higher temperature are known solutions for increasing crystallites size and layers orientation and as a consequence to enhance tensile modulus of carbon fibres. However, an alternative solution is to modify polymeric chains orientation in precursor fibre using a chemical or physical treatment. In this study, polyacrylonitrile (PAN) precursor fibres were prepared using a wet-spinning method and ammonium iron (II) sulphate was added in the coagulation bath as a plasticiser to enhance chains orientation of precursor fibres. A control PAN fibre tow was prepared with the same process variables to compare the effect of chemical treatment. Then, PAN fibres were stretched in a steam bath, stabilised and carbonised. In order to compare chains orientation in chemically treated and untreated fibres, orientation of PAN chains in precursor, aromatic ladders in stabilised and graphite layers in carbon fibres were investigated using a wide angle X-ray spectroscopy (WAXS) technique. Moreover, degree of polymeric chains degradation on cross-section of treated and untreated stabilised fibres were analysed using a mapping IR-spectroscopy technique. Mapping IR-spectra showed a less radial heterogeneity on cross-section of chemically treated fibres and a less thermal degradation ratio. Moreover, orientation of chemically treated precursor was increased from 0.54 to 0.61 and rose from 0.25 to 0.29 in carbon fibres produced from the chemically treated precursor.

159

Origin of high capacity of graphene like graphite anode

Matsuo, Y1, Hashiguchi, K1, Taninaka, J1, Maruyama, S, Sasaki T1, Cheng, Q2, Okamoto, Y2, Tamura, N2


1 University o Hyogo, Himeji, Japan 2 NEC Corporation, Tsukuba, Japan

It has been reported that graphene shows both high capacity and rate performance as an anode of lithium ion battery, however, it suffers from low coulombic efficiency at the first cycle because of its intrinsically high surface area. In this context, we have recently proposed a carbon material named graphene like graphite (hereafter GLG) as a superior anode of lithium ion battery. It is prepared by the thermal reduction of graphite oxide under the condition to avoid exfoliation, therefore, the morphology of it is similar to that of graphite and the surface area is considerably low. It shows not only high capacity and rate performance but also higher coulombic efficiency. In this study, factors affecting the capacity and coulombic efficiency of GLG have been investigated. The capacity increased as the increase in the oxygen content with a slope of Li/O ratio of 3 and reached 670 mAh/g with the cut off voltage of 2 V. Substitution of oxygen in GLG by hydrogen improved the coulombic efficiency. The cell voltage to start the insertion of lithium ions into GLG became lower as the increase in the oxygen content. Large interlayer expansions (～0.1 nm) at the end of charge were observed for GLG with oxygen contents of 0.5 % or more.

160

Oxygen Transfer in Graphite-To-Graphene Oxide Conversion: Simulation Vs. Experiments

Radovic, LR1,2, Mora-Vilches C1, Kaneko K3

[email protected] or [email protected]

1University of Concepción, Concepción, Chile 2The Pennsylvania State University, University Park, PA 16802, USA

3Shinshu University, Nagano, Japan

All the stages of emerging commercial applications of graphene – its preparation, functionalization and utilization – are profoundly affected by interaction with oxygen-containing gases or liquids. Thus, for example, exfoliation of graphite relies on the formation of oxygen surface functionalities at graphene edges as well as its basal planes. Similarly, surface oxygen functionalization is ubiquitous in Fermi-level and band-gap engineering of graphene. And fuel-cell applicability of both pristine and heteroatom-doped graphene (e.g., in the oxygen reduction reaction) is critically dependent on its surface (electro)chemical properties and the efficiency of oxygen transfer. Nevertheless, the essential details of oxygen transfer are both controversial and unclear. Indeed, perusal of the recent literature too often leaves the (arguably wrong) impression that a ‘new’ carbon surface chemistry is necessary to explain the relative virtues of graphene with respect to, say, activated carbons or carbon blacks. Here we present results that highlight the critical issues, especially in the conversion of graphite to graphene oxide: (i) if and when graphene-oxygen interactions occur at edge or basal-plane sites; and (ii) the relative roles of substitutional N and B in oxygen transfer.

161

Performance of Pd/Graphene Oxide Catalysts: Influence of Reduction Degree

Ruiz-García C1, Lei Y2, Heras F1, Elías AL2, Terrones M2, Gilarranz MA1

[email protected]

1 Sección de Ingeniería Química, Universidad Autónoma de Madrid, Madrid, Spain 2 Department of Physics, The Pennsylvania State University, State College, USA

Graphene oxide (GO), obtained by oxidation and exfoliation of graphite, is the most common way to obtain graphene in bulk amounts. Thus, in the last years GO has been widely used to obtain graphene-based materials and composites. GO is hydrophilic, easily dispersible in water and it can be easily functionalized. The aim of this work is to obtain a set of materials based on GO with different degrees of oxidation and decorated with Pd nanoparticles. These materials were tested as catalysts in the hydrodechlorination reaction in the liquid phase. GO was prepared by oxidation and exfoliation of graphite using H2SO4, H3PO4 and KMn2O4, purified, and freeze dried. Metal nanoparticles were prepared by reduction of Pd(AcO)2 with ethanol in the presence of GO (~1.5% Pd/C wt.). Hydrazine monohydrate was used in different quantities and at different temperatures in order to reduce GO. These samples were characterized by X-ray photoelectron and Raman spectroscopy, nitrogen adsorption-desorption, thermogravimetric analysis and X-ray powder diffraction. The reaction tests were performed using 4-chlorophenol as a model compound, under constant hydrogen flow, stirring and mild conditions. The results showed that oxygenated groups in GO clearly enhance the activity of the catalyst and the selectivity to hydrogenation products.

162

Performances Of C/C-Sic Composites Derived from Polyarylacetylenes Containing Silicon

Zheng Jinhuang1, Cui Hong2, Li Hejun1, Yao Dongmei2, Su Hong2, Deng Hailiang2, Yin

Zhongyi2, Zhang Xiaohu2, Wang Kunjie2


1 State Key Laboratory of Solidification Processing, Northwestern Polytechnical University, Xi’an, PR China

2 Xi’an Aerospace Composites Research Institute, Xi’an, PR China Polyarylacetylenes (PAA) has potential advantages as the matrix resin of C/C-SiC composites with high ablation performances, compared with conventional phenolic resins. In this study, the performances of PAA containing silicon (PSAA) were investigated. Two-dimensional carbon fiber reinforced carbon and silicon carbide matrix (C/C-SiC) composites with density of 1.61g/cm3 were prepared by moulding and polymer impregnation pyrolysis (PIP) using PSAA as the matrix precursor. The bending strength, the interlaminar shear strength, the oxidation rate at 1773K, the linear ablation rate and mass ablation rate under oxygen-acetylene flame are 307.8 MPa, 21.32 MPa, 6 %, 0.015 mm/s and 0.0040 g/s, respectively. These results show that PSAA is the excellent matrix precursor of C/C-SiC composites with outstanding anti-delamination, anti-oxidation, and anti-ablation performances at high temperatures. This indicates that the composites derived from PSAA precursor are the potential candidates used as high temperature protection (TPS) materials of space heat shields.

163

Plastic deformation of glassy carbon at high pressure

Shiell, T. B1, McKenzie, D. R2, McCulloch, D. G.3, Field, M3, Haberl, B4, Boehler, R5, and Bradby, J. E1


1The Australian National University, Canberra, Australia 2The University of Sydney, Sydney, Australia

3RMIT University, Melbourne, Australia 4Oak Ridge National Laboratory, Oak Ridge, USA

5Carnegie Institution of Washington, Washington, USA Glassy carbon (GC), also known as vitreous carbon, is a non-crystalline fully sp2 bonded solid which is manufactured by the high-temperature decomposition of certain cross linked polymers. GC resists graphitisation even when annealed to temperatures up to 3000°C, classifying it as a “non-graphitising” carbon material. The unique microstructure of GC leads to a “superelastic” property in which it almost completely recovers its shape after large compressive strains have been applied, such as those arising during indentation experiments. However, the structural origins of this superelastic property are difficult to determine from indentation experiments alone. To understand this superelastic phenomenon, the threshold stress required to induce permanent structural deformation must be found. In this study, we investigate changes in the GC structure when subjected to a non-hydrostatic high pressure environment at room temperature inside of a diamond-anvil-cell. The specific aim of these experiments is to determine a threshold stress for permanent deformation and to observe whether a non-graphitizing carbon such as GC can be converted to a graphitizing carbon by subjecting it to pressure alone. In situ X-ray diffraction measurements show the development of preferred orientation of the graphitic layers perpendicular to the excess uniaxial stress component. Ex situ TEM images and electron diffraction measurements show that permanent preferred orientation is induced when the applied stress is raised beyond a critical level, leading to a loss of the original non-graphitising three-dimensional microstructure.

164

Polarization Effects on Superionic-State of Ionic Liquids in Carbon Nanopores.

Futamura, R1, Iiyama, T1,2, Gogotsi, Y1,3, Salane, M4, Simon, P1,5. Kaneko, K1

[email protected]

1 Center for Energy and Environmental Science, Shinshu University, 4-17-1, Wakasato, Nagano-City, 380-8553, Japan

2 Faculty of Science, Department of Chemistry, Shinshu University, 3-1-1, Asahi, Matsumoto-City, 390-8621, Japan

3 Department of Material Science and Engineering, and A.J. Drexel Nanomaterials Institute, Drexel University, 3141 Chestnut Street Philadelphia, Pennsylvania 19104, USA

4 Sorbonne Universités, UPMC Univ. Paris 06, CNRS, Laboratoire PHENIX, F-75005 Paris, France

5 Université Paul Sabatier, CIRIMAT UMR, CNRS 5085, 5085, 118 route de Narbonne, 31062 Toulouse Cedex 4, France

Supercapacitors with pure ionic liquids as electrolytes are one of the most hopeful

energy storage devices in the next generation because of excellent electrochemical properties of ionic liquids.

Recently, Kondrat and Kornishev [1] predicted that “superionic state”, which they named, could be related to the high capacitance of the supercapacitors because of the effective electrostatic screening on inter-ion interactions by metal-like conductive pore walls of the carbon nanomaterials. In such pores, ions of same charges can be closer each other regardless of the strong repulsive Coulombic interaction. However, the concrete experimental evidence whether such a superionic state exists or not is still not obtained although extensive experimental researches have been conducted for the understanding of ionic liquid inside carbon materials.

Very recently, we succeeded to describe the detailed 3D structures of ionic liquids inside monolayer and bilayer size of carbon nanopores with X-ray scattering aided hybrid reverse Monte Carlo (HRMC) technique, indicating the experimental evidence of the superionic state is formed by ionic liquid in the monolayer confinement [2]. In this work, we show that the unique ionic liquid structure in unpolarized and polarized carbon nanopores with the X-ray scattering aided HRMC simulation. Our results would be directly related to the microscopic origin of the high performance of ionic liquid supercapacitors. [1] S. Kondrat, and A. A. Kornyshev, J. Phys.: Condens. Matter, 23, 022201 (2011). [2] R. Futamura, T. Iiyama, Y. Takasaki, Y. Gogotsi, M. J. Biggs, M. Salanne, J. Ségalini, P. Simon and K. Kaneko, Paper in revision.

165

Predicting long-term behavior of carbon fiber reinforced shape memory polymer composites using acceleration tests

Joon Hyeok Jang1, Seok Bin Hong1, Yongsan An1, Jin-Gyun Kim2, Nam Seo Goo3 and

Woong-Ryeol Yu1


1 Department of Materials Science and Engineering and Research Institute of Advanced Materials, Seoul National University, Seoul, Korea

2 Mechanical Systems Safety Research Division, Korea Institute of Machinery & Materials, Daejeon, Korea

3 Department of Aerospace Engineering, Konkuk University, Seoul, Korea

Carbon fiber reinforced shape memory polymer composites (CF-SMPCs) have been researched for space structural materials due to their high mechanical properties and self-deployment properties. Long-term durability is very important for those materials along with mechanical properties. In the aerospace, in particular low earth orbit (LEO) space region, there are many factors that affect polymer matrix composites. For successful applications of CF-SMPCs to space structural materials, the long-term properties of CF-SMPC in space environments need to be predicted. In this study, CF-SMPCs made of CF and epoxy shape memory polymers were studied, focusing on their life prediction using time-temperature superposition principle (TTSP) and acceleration tests under more severe conditions. The CF-SMPCs were exposed to LEO space environment (high vacuum, ultraviolet radiation and atomic oxygen (AO)) at elevated temperatures in a space environment chamber for accelerated test. Then, their storage modulus was measured using dynamic mechanical thermal analysis. A master curve based on TTSP were constructed to predict the long-term behavior of CF-SMPC in harsh environments. Finally, a degradation model was developed to evaluate the durability of CF-SMPCs in aerospace.

166

Preparation and Properties of Rolled Multiwall Carbon Nanotube Arrays

Eaton, D. L.1, Weisenberger, M. C.1, Andrews, R. J.1

[email protected]

1 University of Kentucky, Center for Applied Energy Research, Lexington, KY, USA

Using our established methods for CVD production of dense, vertically-aligned multiwall carbon nanotube (MWCNT) arrays, we present their preparation on various thin substrates, e.g. metal foils and sub-mm thick borosilicate glass, followed by rolling the arrays through parallel metal compression rollers. The rolling process reorients the MWCNT vertical alignment (z direction) to that of the direction of rolling (x direction). Removal of the substrate, followed by X-ray analysis, enables the examination of the rolled and flattened arrays for nanotube preferred orientation. Mechanical and electrical measurements are presented that allow us to probe the anisotropy of the material. Transmission electron microscopy data are presented of the rolled MWCNT material following heat treatment under graphitization conditions.

167

Preparation and Characterisation of Carbon Spheres for Carbon Dioxide Capture

Sibera D, Narkiewicz U. , Kapica-Kozar J., Serafin J., Michalkiewicz B., Wróbel R.J.,

Morawski A.W. Presenting author’s e-mail: [email protected]

West Pomeranian University of Technology Szczecin, Faculty of Chemical Technology and Engineering, Institute of Chemical and Environment Engineering, Pulaskiego 10, 70-322

Szczecin, Poland

Carbon spheres were prepared by carbonisation of phenolic resin spheres obtained using a modified Stoeber method in a microwave assisted solvothermal reactor. Preparation process involved water-ethanol, ammonia water, resorcinol, potassium oxalate and formaldehyde. The mixture was stirred for 24 hours at room temperature and then subjected to a pressure treatment, in which the solution was treated in a microwave assisted solvothermal reactor for 15 minutes at a pressure of 1 – 3 MPa. The proposed synthesis resulted in a material containing microporous carbon spheres having high surface area (from 1178 to 1648 m2/g), with diameters from 200 to 350 nm, total pore volume from 0.49 to 0.78 cm3/g, and high CO2 adsorption capacity from 3.86 to 5.03 mmol/g measured at 0.1 MPa and 25oC. Taking into account the properties of the obtained material, it can be applied as a sorbent for CO2 capture.

168

Probabilistically based defect analysis with regard to structure-property-relations of CF

Wolz, D. S.1,2, Thieme, M.1,2, Kirsten, M.2,5, Löffler, M.3, Mühle, U.4, Rellinghaus, B.3, Jäger,

H.1,2, Gude, M.1,2, Zschech, E.3, Cherif, C.2,5, Böhm, R.1,2


1 Institute of Lightweight Engineering and Polymer Technology, Technische Universität Dresden, Dresden, Germany

2 Research Center for Carbon Fibers Saxony, Technische Universität Dresden, Dresden, Germany

3 Dresden Center for Nanoanalysis, Technische Universität Dresden, Dresden, Germany 4 Institute of Materials Science, Technische Universität Dresden, Dresden, Germany

5 Institute of Textile Machinery and High Performance Material Technology, Technische Universität Dresden, Dresden, Germany

For novel carbon fibre (CF) applications like porous membranes for desalination and fuel cells or low-cost carbon fibres with high-tensile strengths for carbon concrete composites, the fibre properties need to be tailored which results in structure-property-analysis. Despite tremendous research effort in recent years, this relationship between CF structure and mechanical properties is not fully understood yet. Therefore, tailoring the CF properties is still very limited. It is well known that each content of a CF structure (crystalline and amorphous contents) and defects on different length scales differently contribute to the CF properties. Thus, the effect of defect sizes, volumes and orientations on the CF structure and subsequent the CF properties is analysed by computer tomography and microscopic methods within this study. Special emphasis is given to a 2D and 3D analysis of the distribution of void size and void volume along the CF diameter and the fibre length axis. Correlations between the defect size and volume distributions and measured mechanical properties will be presented. A novel probabilistically-based method will be used for that purpose. The pathway to tailor novel carbon fibres with the generated deeper understanding of the structure-property-relations will be illustrated.

169

Processing and Characterization of Long Fibre Thermoplastic Technology-Based Carbon/Abs Composites

Cho, D, Hwang, D


Department of Polymer Science and Engineering, Kumoh National Institute of Technology, Gumi, South Korea

For the past years, carbon fibre-reinforced plastics (CFRP) with thermoplastic matrices have been increasingly attracted due to their faster processing time, extrusion/injection processibility, and recyclability, particularly in automobile industries. Most recently, long fibre thermoplastics (LFT) technology is of great academic and industrial challenges to produce carbon fibre-reinforced thermoplastics (CFRTP). Extrusion is a useful process to produce the CFRTP with chopped carbon fibres and thermoplastic matrix through compounding, extruding, cooling, and pelletizing processes. During extrusion, however, carbon fibres may be exposed to severe shearing forces occurring between the screws in the extrusion barrel, resulting in fibre breakage and shortening. As a result, the mechanical properties of the CFRTP are deteriorated more than expected, after extrusion and injection moulding. LFT technology has been emphasized as a processing method to solve such the problem. LFT technology-based CFRTP may provide increased stiffness, strength and impact toughness, compared to conventional CFRTP. This is ascribed to the longer fibre length in the matrix of CFRTP without extrusion. An acrylonitrile-butadiene-styrene (ABS) terpolymer is an industrially important, versatile resin because of its high toughness, dimensional stability, surface texture, and processibility. In this study, LFT technology-based carbon fibre/ABS composites are produced with carbon fibre (PAN-based, 12k,) and ABS pellets by using a thermoplastic towpregging machine and their tensile, flexural, impact, and thermal properties, depending on the fibre length of the LFT pellets, are characterized and compared with carbon fibre/ABS composites through extrusion process. The average lengths of the LFT pellets used are 6, 12, and 24 mm.

170

Production of Graphitic-Whisker in Scrolled Natural Polymer Film as "Microreactor"

Saito, Y1, Luchnikov, V2

[email protected]

1 The University of Tokyo, Japan 2 Institute of Materials of Science of Mulhouse, France

The carbon micro-tubes derived from scrolled natural polymers were used as "microreactors" for production of cone-shaped graphitic whiskers (CGWs). CGW is a type of carbon whisker, characterized by a super-helical cone stack of graphene. CGW is easily produced by carbonization of woody plants, especially of silica-rich species, since silica can be converted to SiC via heat treatment and works as nuclei for stable growth of CGW with their apex angles (135-140°). Our previous studies indicated that wood cells work as "microreactors" affecting the shape and size of CGWs grown inside. In this study, we aimed to synthesize CGWs in artificial "microreactors". A film having gradient of moisture-swelling property in the thickness direction was prepared by chitosan, a natural carbohydrate polymer. This film was immersed in water and self-scrolled into a micro-tube, owing to different swelling rate of both surfaces. The resultant chitosan tubes (ca. a hundred μm diameter) were connected to charcoal block, so that the source of carbon and SiC is supplied in the gas state by the charcoal during heat treatment at 2450°C. As the result, CGWs (ca.1 μm diameter and a few hundred μm length) were successfully grown in the artificial microreactors. Using designed microreactors enables further studies to elucidate the function of micro-space and nuclei for growth mechanism, which affects yield and structural fluctuation of CGWs.

171

Production of Nitrogen-Doped Carbon Nanotube Sponges Using Isopropanol as Precursor in The Aacvd Method

Cortés-López, AJ1, López-Urías, F1, Muñoz-Sandoval, E1


1 Instituto Potosino de Investigación Científica y Tecnológica, A.C., San Luis Potosí, México

ABSTRACT Carbon sponge-type structures have attracted special attention due to potential energetic and environment applications [1]. Carbon sponges are superhydrophobic structures, very light, have high surface area, highly porous and could be elastically reversible deformed [2-3]. Furthermore, Carbon sponges could be used to develop of supercapacitor devices, electrodes carbon based, employed as materials to devices and to remove oil and organics contaminants from water [4]. In this work, carbon sponges-type nanostructures based on coaxial nitrogen-doped multiwalled carbon nanotubes were synthesized using the aerosol assisted chemical vapor deposition method involving the decomposition of a mixture of ferrocene, thiophene, and isopropanol at 1020 C under a flow of H2/Ar. Sample morphology and composition profiles were analyzed by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, and thermogravimetric analysis (TGA). REFERENCES

[1] J.G. Yu, X.H. Zhao, H. Yang, X.H. Chen, L.Y. Yu, J.H. Jiang, X.Q. Chen, Aqueous Adsorption And Removal Of Organic Contaminants By Carbon Nanotubes, Sci. Total Environ. (482) (2014) 241-251.

[1]. W. Zhao, C. Shan, A.L. Elias, L.P. Rajukumar, D.J. O’Brien, M. Terrones, B. Wei, J. Suhr, X.L. Lu, Hyperelasticity Of Three-Dimensional Carbon Nanotube Sponge Controlled By The Stiffness Of Covalent Junctions, Carbon (95) (2015) 640-645.

[2]. E. Muñoz-Sandoval, A. Cortes-López, B. Flores-Gómez, J. L. Fajardo-Díaz, R. Sánchez-Salas, F. López-Urías. Sponge-Type Structures Based on Coaxial Nitrogen-Doped Multiwalled Carbon Nanotubes Grown by CVD using Benzylamine as Precursor. CARBON 115, 409-421 (2017).

[3]. W. Chen, R.B. Rakhi, L. Hu, X. Xie, Y. Cui, H.N. Alshareef, High-Performance Nanostructured Supercapacitors on a Sponge, Nano Lett. (11) (2011) 5165-5172.

172

Quinone Molecules in or on Single-walled Carbon Nanotubes for Low Temperature Na Ion Batteries

S. Kawasaki, C. Li, S. Inayama, M. Nakamura, Y. Ishii

[email protected]

Nagoya Institute of Technology, Nagoya 466-8555, Japan We prepared several kinds of quinone molecules encapsulated in single-walled carbon nanotubes (SWCNTs) and also prepared SWCNT samples having polymerized quinone molecules grafted on the outer surface of SWCNTs. We investigated Li and Na ion battery electrode properties of these two kinds of quinone-SWCNT composites at room and low temperatures. Na ion reversible capacity of PhQ encapsulated in large diameter (D = 2.5 nm) SWCNTs measured at low temperature of 0°C was kept as high as that measured at RT, while the capacity of PhQ in small diameter (D = 1.5 nm) SWCNTs at 0°C was about a half of that at RT. The diameter dependence of the capacity should be attributed to the difference in the interactions between the encapsulated PhQ molecules and the host SWCNTs which was revealed by Raman peak profile analysis. Charge-transfer reaction from metallic tubes to PhQ molecules encapsulated in small diameter SWCNTs was detected by Raman measurements. Electrostatic interaction between charged SWCNTs and PhQ molecules induced by the charge-transfer reaction would partly contribute to the stabilization of PhQ molecules in small diameter SWCNTs, while only van der Waals interaction stabilizes PhQ molecules in large diameter SWCNTs. The stability difference was confirmed by TG and XPS measurements. Charge-discharge curve profiles of PhQ encapsulated in SWCNTs were also discussed based on the stability difference.

173

Rapid and Efficient Oxidation Process for Carbon Fibre Production

Bonds, T1, Paulauskas, F2


Affiliations 1 RMX Technologies, LLC, Knoxville, TN, USA

2 Oak Ridge National Laboratory, Oak Ridge, TN, USA

To process precursors for carbon fibre, manufacturers need to first oxidize the material so that it will survive the subsequent carbonization process. Most carbon fibre production uses polyacrylonitrile (PAN) as the precursor. The conventional oxidation process uses very large convection ovens that utilize molecular oxygen from the air to stabilize the fibre for carbonization. This process is energy inefficient and expensive. In general, this technique takes, on average, between 75 to 120 minutes, and is the bottleneck in the production process. Fortunately, a new manufacturing technique has been developed that can oxidize the precursor three times faster than the conventional method. This manufacturing technique, called plasma oxidation, stems from joint research between the Oak Ridge National Laboratory (ORNL) and RMX Technologies that was completed in 2015. Plasma oxidation will lower the cost of carbon fibre and make larger tonnage throughputs a reality. A plasma oxidation oven with a nameplate capacity of 175 annual metric tons of carbon fibre is being readied for operations by the end of 2017. In contrast to conventional ovens, plasma oxidation ovens generate highly oxidative reactive species from the air that react with the precursor much faster than molecular oxygen. This aspect, along with additional design refinements results in a significantly accelerated oxidative process that is more energy efficient, reliable and controllable than conventional oxidation – all while producing final carbon fibre with mechanical properties equivalent or better than conventional. The history of development, technical aspects of the technology and present commercialization work will be discussed.

174

Rational Design of Carbon Materials for Advanced Lithium Sulfur Batteries

F. Li1, R.P. Fang, G.J. Fang, H.-M. Cheng2


Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences

Wenhua Road, Shenyang 110016, China.

Lithium-sulfur (Li-S) batteries are currently being explored intensely due to their high theoretical specific energy density and low cost. However, the areal sulfur loading of electrodes is usually less than 2.0 mg cm-2, which leads to low areal capacity that does not even outperform standard Li-ion batteries, greatly degrading the high-energy advantage of Li-S batteries. Therefore, considering the practical reliability of Li-S batteries, it is of great importance to develop new materials and structures for the cathode that not only allows a high areal sulfur loading, but also enables high sulfur utilization and good cycling stability. In this respect, carbon materials show unique advantages because of their high conductivity and tunable pore structure. Here, we report the facile synthesis of a highly porous graphene as the sulfur host, allowing a high sulfur content of 80 wt%, which further enables a high sulfur loading of 5 mg cm-2. And we obtained a hollow carbon fiber foam through a simple and scalable approach using natural cotton as the starting material, then it was used as a 3D current collector to accommodate sulfur- multi-wall carbon nanotubes - carbon black hybrid within the void space of the conductive scaffold. Our results demonstrate not only facile fabrication of electrodes with high areal loading of sulfur on a 3D carbonaceous current collector, but also novel insight into the mechanism of polysulfide trapping within the cathode, therefore, would be valuable for the fundamental research and possible commercialization of Li-S batteries.

175

Reactive Processing System for Carbon Fibre-reinforced Thermoplastic Polyamide-6 Composites Production

Kim, S1, Seong, D. G1, Um, M1, Park, T1, Yi. J1*


1 Korea Institute of Materials Science (KIMS), Changwon, South Korea

The carbon fibre-reinforced plastic (CFRP) is a promising candidate for aerospace and automotive industries as a high-strength material having desired light-weight. Especially, there are tremendous interests towards automotive parts consisted of CFRP to increase fuel efficiency for clean energy and environment. However so far manufacturing cost of the CFRP, consisted of thermoset like epoxy resin, has been too expensive to be applied to mass production due to time- and cost-consuming curing process. However, thermoplastic CFRP does not require the curing process, which reduces manufacturing cost and cycle time. Also it can be welded or recycled upon melting. Despite the advantages of the thermoplastic CFRP, it is hard to produce with existing resin transfer moulding (RTM) process, owing to the high viscosity of thermoplastic polymer. Therefore, reactive processing has been suggested, where the low viscosity monomer melts instead of polymer melts are injected into carbon fibre fabrics, and following in-situ polymerization enables to produce the thermoplastic CFRP. In this study, our research team developed the reactive processing system for carbon fibre-reinforced thermoplastic polyamide-6 (PA-6) composites production. The in-situ anionic ring-opening polymerization of ε-caprolactam was utilized for PA-6 matrix synthesis. The properties of PA-6 polymer matrix, mechanical properties, and impregnation and interfacial interaction of the CFRP are investigated

176

Regioselective Catalysts for Repair of Graphene Structure From Graphene Oxide

Barkauskas, J1., Gaidukevič, J1., Mališauskaitė, I1., Pauliukaitė, R1,2., Niaura, G2., Astromskas, G2., Bukauskas, V2., Trusovas, R2.

[email protected]:[email protected]

1 Vilnius University, Faculty of Chemistry and Geosciences, Vilnius, Lithuania 2 Center for Physical Sciences and Technology, Vilnius, Lithuania

Graphene oxide (GO) is widely used in energy, optical, electronic and sensor devices as a precursor of graphene. GO precursor can be effectively prepared by chemical methods in large quantities. It possesses different types of oxygen functionalities which allows GO be easily dispersed in organic and inorganic solvents to produce the films and coatings. The process of reconstruction of -conjugated graphene structure from GO is of particular importance for the quality of graphene-based devices. Methods used for the repair of graphene structure are based on the reduction of GO and removal of oxygen functionalities. Despite the recent progress in this area, a high-quality reconstruction of graphene structure from GO precursor is still a problem. The use of regioselective catalysts seems to be a prospective method for this purpose. In the case of GO, the catalyst should be efficient for the epoxy ring opening. The epoxy groups, abundant on GO basal planes, hinder the formation of -conjugated graphene structure. The catalytic effect of H3BO3 and glycerol chelate complex on regioselective epoxide ring opening has been explored in this research. The mechanism of the regioselective reaction was examined by using a laser excitation method. Reduced GO products were analyzed by SEM, XRD, TG/DSC, BET, FTIR, Raman spectroscopy and electrical conductivity measurements. Electrochemical investigation (cyclic voltammetry and EIS) was performed having aim to use the synthesized materials for supercapacitor application. The results obtained show that regioselective H3BO3 – glycerol catalysts are promising candidates for the repair of graphene structure.

177

Removal of Mercury by Activated Carbon In Coal-Fired Power Plant

Jang, H.N.1, Back, S.K.1, Sung, J.H.1, Jeong, M.J1, Seo, Y.C.1


1 Dept. of Environmental Eng., Yonsei University, Wonju, South Korea

The capture of mercury was investigated by powder activated carbon injection at newly operating hybrid filter which is combined with electrostatic precipitator and fabric filter. Even though the operation of the hybrid filter with existing electrostatic precipitator and flue gas desulfurization unit could achieve higher than 90% of mercury removal in total, the injection of powder activated carbon would enhance the efficiency clearly. The injection rate of powder activated carbon was optimized as 200 mg/m3 with hybrid filter operation in the anthracite coal-fired power plant tested. When the injection rate of powder activated carbon increased from 0 to 200 mg/m3, the speciation fraction of elemental mercury significantly decreased from 85.19% to 3.76% with the increase of oxidized mercury fraction. With combined effects of the oxidation and deposition of mercury into powder activated carbon by passing the hybrid filter and of the dissolution by wet scubbing at flue gas desulfurizer, the total removal efficiency could be obtianed greater than 99%.

Acknowledgement

This work is supported by Korea Ministry of Environment as “The Eco-Innovation Project”. This work is also supported by Korea Ministry of Environment (MOE) as Waste to Energy and Recycling / Knowledge-based Environmental Service Human Resource Development Project as well.

178

Rice Husk/Lignosulfonate-Based C/C-Composite For Health and Environment Protection

Jandosov J1,3, Howell C2, Chenchik D3, Kerimkulova A1,3, Bijsenbayev M3, Ray S2,

Mikhalovsky S2, Mansurov Z1,3, Lyubchyk S4, Silvestre-Albero J5,


1 Al-Farabi Kazakh National University, Almaty, Kazakhstan 2 School of Pharmacy and Biomolecular Science University of Brighton, UK

3 Institute of Combustion Problems, Almaty, Kazakhstan 4 REQUIMTE, FCT, Universidade Nova de Lisboa, Portugal

5 Laboratorio de Materiales Avanzados, Universidad de Alicante, Spain In this study, the novel carbon-carbon/ash composite based on rice husk (RH) and Calignosulfonate were synthesized via mixing, extrusion, dry-curing carbonization/physical activation. The AC products was base-leached and/or acid washed, thoroughly washed with distilled water and dried to yield AC/C-ash composite CRH lignosulf@850 and CRH lignosulf@850/demin, respectively. The obtained nanostructured carbonaceous adsorbents were characterized by modern physico-chemical methods of investigation: SEM/EDS, XPS and LTNA. We believe that the following processes may take place during carbonisation/activation of RH/ligno pellets to yield the final AC product: complex process of RH and lignin pyrolysis: carbon burn-off due to thermodynamically allowed (past 700 °C) steam activation reaction, alkaline-earth metal silication and sulfation. XPS-analysis data have suggested that despite the fact that high surface area had been achieved, the remaining ash components of CRH lignosulf@850 composite still contribute to ca.15% of ash: CaSiO3, MgSiO3, CaSO4 and SiO2, while upon acid/base washing, the ash content was reduced to less than 1%. SEM morphology of the obtained composites were characterized by developed structure having both macro- and nanoporosity. According to the calculations based on QSDFT (equilibrium model) the surface areas for the samples CRH lignosulf@850 and CRH lignosulf@850/demin are 1044 m2/g and 1145 m2/g, respectively. CRH lignosulf@850 pellets can be used for volatile organic compounds (VOCs) in gas masks and, on the industrial level to capture toxic VOCs exhausts from industrial plants producing organic products. The use of CRH lignosulf@850/demin granulated composite was designated for future investigation as an effective carbon oral adsorbent for detoxification.

179

Robust Carbon Based Reverse Osmosis Membranes Against Chlorine Degradation: Carbon Nanotubes Incorporation and Nitrogen Doping

Ortiz-Medina, J1, Inukai, S1, Kitano, H1,2, Araki, T1,3, Cruz-Silva, R1, Takeuchi, K1,4, Endo,

M1,4

[email protected]

1 Global Aqua Innovation Center, Shinshu University, Nagano, Japan 2 Kitagawa Industries Co, Kasugai City, Aichi, Japan

3 Research Organization for Information Science and Technology, Tokyo, Japan 4 Institute of Carbon Science and Technology, Shinshu University, Nagano, Japan

Carbon based membranes are produced and evaluated as alternatives for conventional polymeric reverse osmosis (RO) membranes, by means of interfacial polymerization (for composite membranes) and by plasma polymerization (for amorphous carbon membranes). Multiwalled carbon nanotubes-polyamide (MWCNT-PA) composite membranes, and nitrogen doped amorphous carbon (a-C:N) membranes are produced and tested against commonly used chlorine for robustness evaluations, using laboratory scale cross-flow systems for performance assessments, as well as electron and atomic force microscopy, and spectroscopy techniques for characterization. Molecular simulations are carried out for activation energy calculations and charge distribution analysis. It is found that the incorporation of MWCNT into the PA matrix for the composite membranes case, and the preferential formation of specific nitrogen groups within the a-C:N structure, promote an improved resistance against chlorine induced degradation of the carbon based membranes. The underlying mechanism for the enhanced robustness seems to be related to the stabilization of amide and aromatic groups produced by the existence of large and stable carbon sp2 domains in the case of MWCNT-PA membranes, and to the creation of higher proportions of aromatic nitrogen groups, which are stronger against chlorination compared to the amine or amide groups, for the a-C:N membranes. This understanding allows to further control the performance of new developed RO membranes based on carbon nanotubes and a-C:N, enabling their potential commercial application.

180

Scanning Electrochemical Microscopy of Graphene-based Hybrids Interfaces: Insights into Physicochemical Interfacial Processes and Electroactive Site

Distribution

Gupta, S.

[email protected]

Department of Physics and Astronomy and Advanced Materials Institute, Western Kentucky University, Bowling Green, KY 42101, USA.

Surface (and interfacial) chemistry is found in various environments of scientific significance including biomembranes, ocean and atmospheric chemistry and applied electrochemistry. Molecular redox behavior on the surface and at the interface is drastically different than their bulk counterpart. Scanning electrochemical microscopy (SECM) is a powerful tool to investigate interfaces determining ion transfer kinetic rate, diffusion coefficient, imaging topography and electrochemical redox reactions. The significant advantage offered by SECM is its capability of probing chemical information of interfacial electron and ion transfer processes at solid/liquid interface irrespective of substrates. A constant potential is applied to the tip and electrochemical working electrode (i.e. the substrate in electrolyte) to drive reaction in bulk electrolyte solution of redox species (or mediator) to probe the surface of certain thickness of graphene-based hybrids. The local or microscopic cyclic voltammograms, probe approach (current versus tip–substrate distance) curves, 2D and 3D micrographs in feedback mode, were chosen for graphene/CNT, graphene/transition metal oxide as supercapacitors to probe ion adsorption and to map highly electroactive (‘hot spots’) sites. The SECM setup has a resolution of ~40 nm and can locate and relocate areas of interest precisely after a coarse image. We present our findings from viewpoint of reinforcing the roles played by heterogeneous electrode surfaces comprised of graphene nanosheets (conducting)/nanomaterials (semiconducting) via higher/lower probe current distributions. SECM approach curves as well as two dimensional scans elucidated the existence of regions of different conductivity and the data is analyzed in terms of edge plane defects distribution within the probes regions, determining diffusion coefficient and heterogeneous rate constant.

181

Separation of Cone-Shaped Graphitic Whiskers by Density Gradient Centrifugation

Goto, Y1., Saito, Y1

[email protected]

1 The University of Tokyo, Japan

Cone-shaped graphitic whiskers (CGWs) comprise highly ordered continuous hexagonal layers stacked in a helical–conical manner. CWGs are a type of pyrolytic carbon derived from carbonaceous materials heated at >2000°C in the presence of nuclei, e.g., SiC, that can act as a trigger for stable growth with their apex angles (135–140°). CGWs are inevitably formed in amorphous carbon and SiC residues and still remain after contributing to the growth of carbon sources and nuclei, respectively. In this study, CGWs were successfully separated from residues via centrifugation in gradients of a haloalkene solvent. The separation was confirmed via the visual formation of a colored band at a density of 1.9–2.0 g/cm3. The amorphous carbon residues became supernatant, and the SiC residues precipitated. It is noteworthy that the observed density of CGWs in the solvent was apparently lower than that calculated (i.e. 2.2 g/cm3) based on the lattice parameters obtained via electron diffraction. Precise investigations using solvent-exchange methods revealed that the frill-like structure covering the surface of CGWs applied a buoyant force and decreased the apparent density of the solvent. Our result shows that the density-gradient centrifugation method successfully separated CGWs. Although their structure is unique, their properties have not been thoroughly investigated, especially for applications in which the analysis requires large amounts of pure samples. This nondestructive method can be further applied to fine and scaled-up separation to reveal their unique properties.

182

SnS2/reduced graphene oxide nanoribbon paper as free-standing anode for SIBs

Yang Liu1, Xuzhen Wang1,2,*, Yongchao Tang2, Zongbin Zhao2, Jieshan Qiu2


1. School of Chemistry, Dalian University of Technology, Dalian, China. 2. State Key Lab of Fine Chemicals, Liaoning Key Lab for Energy Materials and Chemical

Engineering, PSU-DUT Joint Center for Energy Research, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China.

Ultrafine SnS2 nanocrystals/reduced graphene oxide nanoribbon paper (SnS2/RGONRP) has been constructed through a well-designed process including anchoring SnO2 nanoparticels onto graphene oxide nanoribbons (RGONRs) via in situ reduction, evaporation induced self-assembly and sulfuration procedures. The as formed SnS2 nanocrystals possess an average diameter of 2.3 nm and disperse on the surface of RGONRs uniformly. The capillary force during evaporation leads to a compact assembly of RGONRs to give flexible paper structure with high density of 0.94 g cm-3. The as-prepared SnS2/RGONRP could be directly used as free-standing electrode for sodium ion batteries. Due to the synergistic effects between the ultrafine SnS2 nanocrystals and the conductive, tightly connected RGONR networks, the composite paper electrode exhibits excellent electrochemical performance. As high volumetric capacity of 508-244 mAh cm-3 could be obtained at current densities in the range of 0.1-10 A g-1. And discharge capacity of 334 and 255 mAh cm-3 were still kept even after 1500 cycles tested at current densities of 1 and 5 A g-1, respectively. And the evaporation induced self-assembly strategy may also be used to construct free-standing electrodes for other energy storage devices like lithium ion batteries, lithium sulfur batteries and supercapacitors.

183

Solid-State Growth of Carbon-Supported Ceramic Nanostructures For Electrocatalysis

Wang, DW, Xiao, KF, Amal, R


University of New South Wales, Sydney, Australia A simple and cost-effective route for the synthesis of metal nitride and carbide nanowires is reported. A metal-doped polymer was used as the sole precursor. The polymer supplies either nitrogen or carbon sources to forming nitride and carbide via a solid-state thermal carburization/nitriding treatment. This method is more convenient for the sake of the easy-to-prepare precursor and the one-step thermal annealing. The structures of the annealed products are temperature dependent. Combining XRD and XPS analysis, we found that the metal oxide precipitates at low temperature and converts to nitride at or carbides when temperature is raised up. This observation shows the temperature-modulated solid state conversion process. Both SEM and TEM revealed the nanostructures. The products showed improved activity for hydrogen evolution reaction with smaller overpotential comparing to the case without the nanostructured ceramic phases. It is also noticed that the ceramic components played a significant role in stabilizing the precious metal catalyst. The dual function of this new carbon/ceramic material, i.e. as either active catalyst or catalyst support, is promising for future new energy technologies.

184

Solvent Solubility Parameter Dependent Homogeneity and Gelation of Polyacrylonitrile Solutions

Li, W; Liu, Y; Lu, C


National Engineering Laboratory for Carbon Fiber Technology, Institute of Coal Chemistry, Chinese Academy of Sciences, 27 Taoyuan South Road, Taiyuan 030001, P.R. China

The rheological behaviors of polyacrylonitrile (PAN) solution are critical for its spinnability and the mechanical properties of the resultant carbon fibers. In this study, the solution homogeneity and sol-gel transition of PAN solutions in various solvents were characterized by rheological measurements, and the correlations between solvent solubility parameters and rheological behaviors of PAN solutions were proposed. The solution homogeneity was found to be directly related to the HSP distance (Ra) of the solvent. A smaller Ra of the used solvent, a better homogeneity and less PAN chain entanglements in the prepared PAN solution. Additionally, we found that both heating and cooling induced gelation of PAN solutions had strong dependence on the polar parameter of the solvent, but with different gelation mechanisms. No chemical reaction occurred during heating induced gelation, and the deepened color of the PAN solution was ascribed to the formation of nitrile-nitrile structure. A higher solvent polarity would lead to a higher heating induced gelation temperature. Whereas, solvent bridge was the proposed gelation mechanism during cooling, and a higher solvent polarity would promote the formation of the bridge structure and led to a higher gelation temperature. Our results not only help researchers to better understand the rheological properties of PAN solutions, but also provide a convenient method to adjust the chain entanglements and the thermal induced sol-gel transition temperature of PAN solutions by tuning solvent solubility parameters.

185

Specific Interaction-Mediated Efficient Separation of Molecules Through Graphene Nanowindows

Vallejos-Burgos, F1, Kaneko, K1

[email protected]

1 Center for Energy and Environmental Science, Shinshu University, Japan

Separation of gases using distillation is one of the most energy-demanding technologies in the world. It is then needed to find breakthrough technologies that do not depend on phase changes to separate gases. In this sense, highly-selective membrane separation offer an efficient alternative. A novel and unconventional membrane can be made in a graphene layer if we are able to perforate nanowindows in its graphene sheet. Due to its one-atom thickness, it has the advantage of negligible diffusion path for molecules, and thus ultrafast permeation. The chemically active edges of the nanowindow rim induce essentially specific interactions with different gases, which can be exploited to achieve highly efficient separations. We will show how the behaviors of N2, O2, Ar, H2O, CH4 and CO2 near graphene nanowindow rims can be manipulated to separate different mixtures of industrially-relevant gases. Specifically, the roles of functional groups, nanowindow rim vibration and electrostatic field are elucidated.

186

Stretchable Graphene Membranes For Next-Generation Protective Uniforms

Chen, P1, Spitz, R1, Liu, M1, Wong, I1, Hurt, R1


1 Brown University, Providence, Rhode Island, United States

High stretchability is a critical requirement for protective clothing to allow the personnel to move quickly when he/she is engaged in missions in contaminated environments. Current protective uniforms are based on heavyweight full-barrier protection or permeable adsorptive protective garments that cannot meet the critical demand of simultaneous high stretchability and protection. Herein, we will present a higher dimensional graphene-based protective barrier with high stretchability, versatile functionality, and ability to provide an active response to manage an environmental risk. First, we have fabricated highly textured graphene oxide (GO) membranes via mechanical deformation. The surface instability results in out-of-plane bending instead of in-plane compression and creates complex surface topographies (e.g., periodic wrinkles or disordered crumples) on GO membranes. This convoluted graphene structure can provide high stretchability to ~1600% and tolerate reversible mechanical actuation over 500 times, enabling personnel to move quickly without any constrains from the uniforms. Also, the stretchable GO membranes with intrinsic multilayered structures can block over 10 different organic solvents and serve as high-performance barrier coatings even under different stretching states (from 400% to 1500%). We have demonstrated that GO membranes provide at least over 6-order higher full-barrier performance than thick rubber layers. Furthermore, the GO barrier layers can be chemically functionalized and infiltrated with responsive polymers; the graphene-polymer composite materials can be applied into stimuli-responsive electronics that can sense the presence of toxic solvents, diagnose the type of toxicants, and allow the structural change to respond to chemical threats.

187

Strong, twist-stable carbon nanotube yarns and muscles by high temperature tension annealing

Di, J1


1 Division of advanced nanomaterials, Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, Jiangsu 215125, China

We here report a process for stabilizing both twisted and coiled CNT yarns with respect to irreversible untwist, thereby avoiding the need to tether torsional and tensile artificial muscles, and increasing the mechanical loads that can be moved by these muscles. This ITAP (Incandescent Tension Anneal Process) involves thermally annealing twisted CNT yarns at a temperature of about 2000 C while these yarns are under tensile loads. Depending upon the density of the precursor yarn, the ITAP increased yarn modulus and yarn strength by factors of up to 12 and 2.6, respectively. While a non-tethered pristine yarn immediately undergoes irreversible untwist when strained by a freely rotating weight, a non-tethered ITAP yarn can be reversibly actuated by cyclic vapour sorption/desorption to rotate a 6100 times heavier rotor by 52 degree per millimeter of muscle length, thereby achieving a peak rotation speed of 160 revolution per minute. In addition, the ITAP increased yarn stability to oxidation in air at 500 C and conferred remarkable long-term resistance to chlorosulfonic acid, whose protonation ability causes pristine yarns to swell, disorder, and mechanically fail within minutes.

188

Structural Control of 3D Graphene Super-Capacitor Electrodes via Additive Manufacturing

Sherrell, P. C1, Beirne, S2, Wallace, G. G2, Mattevi, C1


1 Imperial College London, London, United Kingdom 2ARC Centre of Excellence for Electromaterials Science, University of Wollongong,

Wollongong, Australia

Macro-scale devices for energy storage and conversion systems based on graphene have developed in two fabrication approaches: formation of hydrogel or aerogel constructs based on reduced graphene oxide and chemical vapour deposition (CVD) of graphene on 3-dimensional (3D) preformed architectures. Structuring graphene into 3D architectures allows for the utilization of graphenes exceptional electrical and mechanical properties. CVD on 3D metal foams has been shown to produce high quality free-standing graphene architectures, however, devices have been stymied by the poor level of structural control over these preformed metal, and subsequent final graphene architectures. Combining additive manufacturing techniques such as selective laser melting (SLM) with CVD we are able to produce free-standing 3D graphene architectures with a controllable macro-structure. The structures are highly conductive with a large free volume ideal for use as electrochemical devices. As electrochemical super-capacitors these materials demonstrate extremely rapid charging and discharging with a τ1/2 as low as 0.7 ms in organic electrolytes allowing for stable cycling at 20 Hz for over 10000 cycles. Through utilization of the van der Waals interactions of graphene with other 2D materials such as transition metal dichalcogenides this large free volume is filled to increase the energy and powder densities of our 3D graphene architectures as well as allowing the exploitation of photo-catalytic energy conversion.

189

Structural prediction of carbide-derived carbons using Molecular Dynamics

De Tomas, C1, Suarez-Martinez, I1, Vallejos-Burgos, F2, Lopez, M J3, Kaneko, K2, Marks, N A1


1 Curtin University, Perth, Australia 2 Shinshu University, Nagano, Japan

3 Universidad de Valladolid, Valladolid, Spain

Carbide-derived carbons (CDCs) are an important class of nanoporous carbons with numerous applications, including supercapacitors, gas storage and selective sorbents. The advantage of CDCs over other porous materials is that the pore size distribution is narrow and tunable through the choice of precursor material and processing conditions. Atomistic models of CDCs are valuable from both a conceptual and a practical point of view, but are non-trivial to construct due to the complexity of carbon bonding. Historically, many different approaches have been used to construct CDC models, ranging from highly idealized structures based on graphene sheets to more sophisticated simulation approaches using either reconstructive or mimetic methods. Mimetic methods are in-principle superior to reconstructive methods because they are predictive, but in practice mimetic methods struggle to accurately reproduce the experimental conditions. In particular, previous mimetic simulations have not reproduced important structural features related to graphitization. Here, a new mimetic methodology is developed to generate atomistic models of CDCs using Molecular Dynamics and the Environment Dependent Interaction Potential. This approach reproduces all the main characteristics of experimentally-prepared CDCs, including microstructure, porosity at the nanometre scale, and graphitization with increasing temperature. Synthesis temperatures are correlated to the simulation annealing conditions using an Arrhenius approach, overcoming one of the main obstacles of previous models. The method is reliable, easy to implement, and enables a fast exploration of adsorption properties of CDCs, making it applicable to design new materials.

190

Study of a Carbon Preform in a Nitrogen Plasma Torch

Vignoles, G. L.1, Lamboley, X.1, Blaineau, P.1, Turchi, A.2, Chazot, O.2, Bianchi, D.3


1University of Bordeaux, LCTS, Pessac, France 2Von Karman Institute for Fluid Dynamics, Rhode-Saint-Genèse, Belgium

3“La Sapienza” University, Rome, Italy

A class of heat shields for atmospheric entry of space objects makes use of insulating refractories like carbon fiber preforms consolidated by a small amount of carbonized phenolic resin. These ~80% porous ablators display exceptional thermal and chemical properties. In order to improve their design, we propose a joint experimental and modeling approach to capture their behavior during operation. Here we focus on the determination of the fiber-scale reactivity of the preform with respect to nitrogen plasmas. Samples have been tested in a nitrogen inductively coupled plasma at 1.5 kPa pressure, and experienced surface temperatures ranging from 1500 to 2800 K. The recession rate has been measured in-situ and the local flow conditions have been reconstructed numerically from experimental data. The structural details of the porous medium have been acquired by X-ray Computerized Micro-Tomography (CMT); then, image-based numerical simulations of ablation by nitridation, with simultaneous occurrence of nitrogen catalytic recombination at the fibers surface, give access to quantification of the reaction rates from the knowledge of the overall recession velocity and of the depth of the affected zone. A simple analytical model is derived to interpret these results.

191

Superactivated Carbons for High Energy Supercapacitors

Diez, N1, Mysyk, R1, Goikolea, E1, Carriazo, D1,2.


1 CIC EnergiGUNE, Miñano, Spain 2 IKERBASQUE, Basque Foundation for Science, Bilbao, Spain

Porous carbons are the preferred materials for the fabrication of electrodes for supercapacitors due to their relatively high electronic conductivity, low cost, inertness, high specific surface area and the possibility to fit their porosity with the sizes of the electrolyte ions. Sophisticated synthesis of carbons with hierarchical porosities involves the use of templates and multi-step synthesis using costly precursors, which make them difficult to scale up. On the other hand, advanced nanostructured carbons such as carbon nanotubes, graphene-based materials or onion-like carbons have moderate surface area and a high production cost by complex synthetic processes, which also hinders their use in supercapacitors. In this work we report the preparation of porous carbons with specific surface areas > 3000 m2 g-1 and tuned porosities by a simple all-in-one route involving simultaneous polymerization, carbonization and in-situ chemical activation of a mixture of melamine and terephthaldehyde. The materials were tested as electrodes for symmetric supercapacitors using aqueous electrolytes (avoiding the exhaustive drying of carbons and moisture-free atmosphere during cell assembly), some of them allowing cycling at voltages far above the thermodynamic stability of water. The superactivated carbons provided capacitance values up to 360 F g-1, very fast response and excellent cycling performance in 6M KOH and 1.2V, being suitable candidates for high power applications. Carbons with hierarchical micro-mesoporosity allowed achieving very high energy densities of 40 Wh kg-1 working in 5M LiTFSI at 2.2V, and 16 Wh kg-1 using 1M Li2SO4 and a voltage window of 1.8V.

192

Surface Modification of Graphene and Graphene Oxides By Nitrogen Plasma: Determination of Chemical State Alterations By Quantitative X-Ray Photoelectron

Spectroscopy

Berke, B1,2, Bertóti, I3, Mohai, M3, László, K1


1 Budapest University of Technology and Economics, Budapest, Hungary 2Institute Laue Langevin, Grenoble, France

3Research Centre for Natural Sciences, Hungarian Academy of Sciences, Budapest, Hungary

The various applications of nanocarbon materials including graphene and graphene oxides often require surface modification, which explains the great effort that has recently been devoted to such investigations. Radio frequency (RF) cold plasma activation is a simple method for initiating gas-solid reactions to modify the surface by exciting, and also partly ionizing, the gas phase reactants. This method enables one to implant the gas atoms into the sub-surface atomic layers, accommodating them in interstitial, substitutional lattice sites or in vacancies. In this work thin films of graphene, graphene oxide and reduced graphene oxide were treated by low pressure RF N2 gas plasma, nominally at room temperature. The amounts of implanted nitrogen and oxygen were determined by quantitative X-ray photoelectron spectroscopy (XPS). Their chemical bonding to the carbon matrix was also investigated in detail. A model was developed to calculate the surface enrichment of nitrogen in the top atomic layers of the samples. Nitrogen plasma treatment resulted in significant reduction (i.e, removal of oxygen) and at the same time, nitrogen incorporation. Three different chemical bonding states of the nitrogen were defined for all treated samples and assigned to pyridine-type and to N in pyrrole-type ring structures, and to N substituting carbon in a graphite-like environment. The nitrogen content, up to 10 at %, was influenced by the initial sample composition and the treatment conditions (bias, time).

193

Surfactant-free single-layer graphene in water, “Eau de Graphene”

George Bepete1, Eric Anglaret2, Carlos Drummond, Alain Penicaud1*

1 CNRS, Centre de Recherche Paul Pascal (CRPP) and University of Bordeaux, F-33600 Pessac, France.

2University of Montpellier-II, Laboratoire Charles Coulomb (L2C), UMR CNRS 5521, F-34000 Montpellier, France.

* [email protected]

Graphite intercalation compounds can be readily exfoliated down to single layers in aprotic solvents due to the favorable entropic contribution of dissociating counterions, yielding graphenide solutions. [1] The resulting graphenide solutions are prone to re-aggregation after oxidation and must be handled in a dry, oxygen-free environment. In this work we describe a "beautifully simple and neat" way to prepare a water solution of single-layer only graphene without adding surfactant. Homogeneous air-stable dispersions of single layer graphene in water with no surfactant added can be obtained by mixing air-exposed graphenide solutions in tetrahydrofuran (THF) with previously degassed water and evaporating the organic solvent.[2-5] Aggregation usually prevents dissolution of graphene in water, we show that, hydroxide ion adsorption on graphene flake surface allow the stabilization of true single-layer graphene in water — with no surfactant required — so long as the liquid is degassed beforehand.[2] In situ Raman spectroscopy of this single layer graphene in water show bands at 1343, 1586, 1620 and 2681 cm-1 corresponding to the D, G, D’ and 2D bands of graphene respectively. The 2D band at 2681 cm-1 is well fitted with a sharp lorentzian line (∼28 cm-1) which is a hallmark of single layer graphene.[3] Coatings on glass substrates from these graphene dispersions have conductivities of up to 30 kS/m.[2] REFERENCES 1. Pénicaud, A., & Drummond, C. (2012).Accounts of Chemical Research, 46(1), p129-137. 2. Bepete, G., Drummond, C., & Penicaud, A. (2015). U.S. Patent Application No. 15/318,173. 3. Bepete, G., Anglaret, E., Ortolani, L., Morandi, V., Huang, K., Pénicaud, A., & Drummond, C. (2017). Nature Chemistry. 9, p347–352 4. Bepete, G., Pénicaud, A., Drummond, C., & Anglaret, E. (2016). The Journal of Physical Chemistry C., 120 (49), p28204–28214 5. Bepete, G., Hof, F., Huang, K., Kampioti, K., Anglaret, E., Drummond, C., & Pénicaud, A. (2016). ” physica status solidi (RRL)-Rapid Research Letters, 10(12), p895-899.

194

Synchrotron Saxs/Waxs Study of Microstructure Evolution In Carbon Fibre Production

Lynch, P1 2, Creighton, C1, Hawley, A3, De Jonge, M3, Mudie, S3, Naghashian, S1, Fox, B4


1Carbon Nexus, Institute for Frontier Materials, Deakin University, Geelong, Australia 2 CSIRO, Manufacturing Flagship, Geelong, Australia

3 Australian Synchrotron, 800 Blackburn Rd, Clayton, Victoria, Australia 4 Factory of the Future, Swinburne University, Hawthorn, Victoria, Australia

Understanding the role of fibre processing, microstructure and relative impact on fibre strength at the level of commercial scale carbon fibre production represents a grand challenge. To address this challenge, development of an empirical fibre structure model is presented. A dedicated synchrotron Small Angle Scattering (SAXS), Wide Angle Scattering (WAXS) fibre testing capability has been developed on the SAXS/WAXS beamline at the Australian synchrotron facility. The experimental design has been optimised for measurement of poorly scattering monofilament fibres with relatively short acquisition times. By measurement of monofilament data, the scattering cross-section is known. Under these conditions, fibre microstructure evolution at any point on the carbon fibre line can be measured precisely. The proposed fibre model comprises a basic structural unit where its microstructure is derived primarily from X-ray scattering data. The basic structural unit and its evolution is then quantified in terms of the crystallographic structure/orientation, the amorphous behaviour and finally the micro-pore size and alignment. As a test example, analysis of monofilament X-ray scattering data is presented for fibres taken across the entire Carbon Nexus 110ton carbon fibre line (Deakin University). This included measurements at the following points on the line: the initial PAN fibre; Stabilisation Zone 1 (passes 1-6); Stabilisation Zone 2 (passes 1-5); Stabilisation Zone 3 (passes 1-6); Stabilisation Zone 4 (passes 1-5); Low temperature furnace; and high temperature furnace.

195

Synthesis and Application of the Ordered Functional Mesoporous Polymer and Carbon Materials

Zhao, Dongyuan


Lab of Advanced Materials and Collaborative Innovation Center of Chemistry for Energy Materials, Fudan University, Shanghai 200433, China

Department of Chemical Engineering, Monash University, Clayton VIC3800, Australia

Engineering polymeric materials, in particular ordered mesoporous polymers with

controllable structure and chemistry, is critical for a large variety of applications. The synthesis of ordered mesoporous organic polymers or their carbon derivatives via interfacial organic-organic co-assembly of the soft templates and organic building oligomers (e.g. phenolic, glucose, dopamine) is one of the most efficient methods to tailor the porous structure and surface property. Here, we present recent progresses and some new insights into the interfacial assembly and engineering on the synthesis of ordered functional mesoporous polymer and carbon materials. Series of new synthesis strategies have been developed based on the interfacial assembly of structure-directing agents and the organic building oligomers, including solvent evaporation induced aggregation assembly, ligand-assisted co-assembly, self-assembly of mono-micelle, interface-induced co-assembly, template carbonization and carbon-supported crystallization. The amphiphilic block copolymers with controllable molecular weights and compositions can also be prepared and applied as templates for ordered mesoporous polymer and carbon materials with many unique features including various mesostructures and framework compositions, ultra-large pores, thick pore walls, high thermal stability and well-crystalline frameworks. Based on these efficient strategies, the derivative mesoporous materials based on the ordered mesoporous polymers with different framework compositions can be well fabricated from pure organic polymers to organic/inorganic hybrids, inorganics, carbon, carbon/inorganic hybrids etc. The obtained ordered mesoporous carbon materials with uniform and controllable pore channels, high surface area, large pore volume, open and tunable frameworks showing great potential applications on in catalysis, energy conversion and storage, adsorption and separation, sensor, biomedicine etc.

196

Synthesis and Characterization Of Biomimetic Carbonated Calcium-Deficient Hydroxyapatite On Carbon Fiber Cloth

Olivier, F1, Picard, Q1, Delpeux, S1, Fayon, F2, Chancolon, J1, Warmont, F1, Rochet, N3,

Bonnamy, S1


1CNRS, Univ. Orléans, ICMN UMR 7374, F-45071 Orléans, France 2CNRS, CEMHTI UPR 3079, Univ. Orléans, F-45071 Orléans, France 3 CNRS, INSERM, Institut de Biologie Valrose, F-06107 Nice, France

Due to their breathability, specific mechanical properties and biocompatibility, carbon fiber clothes have previously been considered tissue engineering. However, its poor biological activity limits its extensive use in medical applications and therefore needs to be enhanced. Conversely, owing to high biocompatibility, bioactivity, and osteoconductivity, calcium orthophosphate (CaP) ceramics have received much attention and have been clinically employed either as coating or as scaffold in orthopaedics. In this context, CaP-coated carbon fiber cloth, combining the high biocompatibility, osteoconductivity and bioactivity of CaP with the properties of carbon fibers, appear as promising biomaterials for bone repair and regeneration. In this work, CaP coating are obtained by sono-electrodeposition process using cathodic polarization. FTIR, HRTEM, SEM and 31P MAS NMR were performed to characterize CaP deposits. Three main types of deposits obtained through variation of electrochemical parameters were elaborated. At low current densities and at constant potential (-1V) the deposit consists in a biomimetic plate-like carbonated calcium-deficient hydroxyapatite (CDA), while at higher current densities the synthesis leads to a needle-like carbonated CDA. At intermediate current density, a mixture of plate-like and needle-like carbonated CDA is deposited. A thorough investigation of the CaP characteristics have shown that the deposition mechanism depends on the electrolysis rate. This established that sono-electrodeposition is a versatile process allowing tuning the morphology of the CaP cotatings, thereby bringing new insights in the development of new biomaterials for bone repair. The materials biocompatibility was determined by culturing primary human osteoblast-cells (HOST) in contact with CaP/carbon cloth hybrid materials.

197

Synthesis and electromagnetic wave absorbing property of amorphous carbon nanotube networks on a 3D graphene aerogel/BaFe12O19 nanorod composite

Tingkai Zhao, Xianglin Ji,*, Wenbo Jin, Alei Dang, Hao Li, Tiehu Li


State Key Laboratory of Solidification Processing, Shaanxi Engineering Laboratory for Graphene New Carbon Materials and Applications, School of Materials Science and

Engineering, Northwestern Polytechnical University, Xi’an 710072, China

Homogeneous amorphous carbon nanotube (ACNT) networks have been synthesized using floating catalyst chemical vapor deposition method on a three-dimensional (3D) graphene aerogel (GA)/BaFe12O19 nanorod (BNR) composite which prepared by a self-propagating combustion process. The as-synthesized ACNT/GA/BNR composite which have 3D network structures could be directly used as a good absorber in the electromagnetic wave absorbent materials. The experimental results indicated that the maximum absorbing peak of ACNT/GA/BNR composite with a thickness of 2 mm was -18.35 dB at 10.64 GHz in the frequency range of 2-18 GHz. The bandwidth of the reflectivity below -10 dB is 3.32 GHz. The 3D graphene aerogel structures which composed of dense interlined tubes and amorphous structure of ACNTs bearing quantities of dihedral angles could consume the incident waves through multiple reflection and scattering inside the 3D web structures. The interlinked ACNTs have both the virtues of amorphous CNTs (multiple reflection inside the wall) and crystaline CNTs (high conductivity), consuming the electromagnetic wave as resistance heat. ACNT/GA/BNR composite has a good electromagnetic wave absorbing performance.

198

Synthesis Of Carbon Nanotubes By CVD on a Shungite Substrate

Nazhipkyzy, M1,2, Temirgaliyeva, T.S1,2, Zhaparova, A.A1.2, Nurgain, A1.2, Lesbayev, B.T1.2, Prikhodko, N.G1, Mansurov, Z.A1,2

[email protected]

1Institute of Combustion Problems, The laboratory “Synthesis of carbon nanomaterials in

flame”, Almaty, The Republic of Kazakhstan 2Al-Farabi Kazakh National University, Faculty of chemistry and chemical technology,

Department of chemical physics and material science, Almaty, The Republic of Kazakhstan

CNTs have unique electronic properties, which can be used to make nanoelectronic devices such as transistor, lithium ion batteries and they have excellent field emission properties such as low emission threshold, high emission current density, and high stability. So it can be used to make high performance flat panel display. CNTs as composite fiber reinforcement can be expected to exhibit excellent strength, fatigue resistance and elastic, isotropic properties. In addition, CNTs have outstanding adsorption properties, such as high efficient hydrogen storage. These specific properties indicate that CNTs have broad application prospects in many areas. Among several techniques of CNT synthesis available today, chemical vapor deposition (CVD) is most popular and widely used because of its low set-up cost, high production yield, and ease of scale-up. Carbon nanotube composites were grown by one-step ambient pressure CVD. In our study, we use a catalytic CVD. The growth process was performed via the catalytic decomposition of propane-butane gas mixture on a shungite substrate with a previously prepared catalyst. High purity propane-butane gas mixture was selected as carbon source. In other experiments, hydrogen used as a reducing agent, in this case, as a reducing agent served carbon that is contain shungite.

199

Synthesis of CuS/Three-Dimensional Graphene for Remarkable Rate Permormance Flexible Supercapacitor

Tian Z1, Zhang B1,Wang YZ1, Zhang HX1,2, Kang LT1,2, Wang XM1,2


1College of Materials Science and Engineering, Taiyuan University of Technology, 030024, PR China 2Collaborative Innovation Center of Green Energy Materials and Energy Storage Systems, Taiyuan University of Technology, 030024, PR China Flexible solid-state supercapacitor (FSSC) has received widespread attention as a promising candidate for energy storage due to its superior performance and safety. However, how to improve the energy density by choose the ideal electrode materials is still a challenge. In this work, we presented a strategy by anchoring CuS on three-dimensional graphene (3DG) via a facile method. Microstructure observations shows that the CuS with tiny nanoplates was successfully obtained. The electrochemical performances of CuS/3DG composite was studied in 3 M KOH electrolyte. The results reveal that the capacitance value of CuS/3DG composite was about 481 mF cm-2 at the current density of 1 mA cm-2 and the specific could maintain 73％ of its initial specific capacitance as the current density up to 20 mA cm-2, suggesting excellent rate performance. Meanwhile, a flexible solid-state supercapacitor was assembled by CuS/3DG, 3DG and PVA/KOH as positive, native and electrolyte, respectively, which exhibited high energy density of 21 W h kg-1 and power density of 75 kW kg-1.This outstanding electrochemical performance may be contribute to the synergistic effect of the CuS and 3DG matrix and this work could provide a new proposal for flexible solid-state energy devices. This work was supported by the National Science Foundation of China (No. 51572184 and 51372160).

200

Synthesizing narrow diameter distributed carbon nanotubes using Fe-implanted wafers

Lee, C-H1, Lee, J2, Lee, S-H1 Lee, K-H1

[email protected]

1 Pohang University of Science & Technology, Pohang, South Korea

2Korea Institute of Science and Technology, Wanju-gun, South Korea

Carbon nanotube (CNT) forest is a collection of aligned CNTs. CNT forest is typically grown from a catalyst-coated wafer. As a catalyst, thin layer of Fe is deposited, which forms tiny particles at high temperature because agglomeration minimizes the surface energy. It is hard to control the degrees of agglomeration that can cause the non-uniform sized catalyst particles. They result in CNTs forests that have broad CNT diameter distribution. Here, to overcome the non-uniformity in the diameter of CNTs, we propose a method to grow CNT forest using Fe-implanted wafer.

In the case of Fe-implanted wafers, Fe particles are located in the wafers and particles can diffuse to the surface during the annealing. The diffused particles are the role of CNT growth seeds. The diameter of diffused Fe particles was maintained during 15 min (13.01 ± 8.82 nm), 1 h (11.95 ± 7.15 nm), 4 h (13.52 ± 8.18 nm) and 12 h (12.91 ± 7.25 nm) annealing. The reason of catalyst particles diameter maintenance is that Fe particles do not diffuse to the surface fully and non-exposed part of particles are stuck firmly in the wafers. This phenomenon can prevent the particles movements. Therefore the diameter of CNTs from implanted wafers could be narrow distributed and maintained during 15 min (7.40 ± 1.54 nm), 1 h (8.85 ± 2.59 nm), 4 h (8.55 ± 2.14 nm) and 12 h (8.67 ± 2.55 nm) annealing. This method opens a way to produce narrow diameter distributed CNTs.

201

Tailoring Few-Layer Graphene for Enhanced Specific Capacitance Applications Using a Hydrogen in Argon Mixed Plasma

Smith, E A M1,2, Crean, C1, Slade, R1, Spacie, C2, Stirling, C2, Watson, D1

[email protected]

1 University of Surrey, Guildford, Surrey UK 2 Haydale Ltd, Ammanford, Carmarthenshire UK

Supercapacitors (ultracapacitors, electrochemical capacitors) are a well-suited energy storage technology utilising highly porous carbons, especially those with tailor-made surface functionalities providing pseudocapacitance additional to otherwise existing double layer capacitance. Commercially available few-layer graphenes with a specific surface area of ca. 700 m2 g-1 were characterised using scanning transmission electron microscopy, electron energy loss spectroscopy and scanning electron microscopy. These few-layer graphenes were plasma treated using a hydrogen in argon gas mixture and Haydale Ltd’s HDPlas® process. The implemented process changed the material’s surface properties, which were characterised by X-ray photoelectron spectroscopy, acid-base titration, zeta potential determinations, moisture content analysis and Raman microscopy. Employing these tailored materials in aqueous supercapacitor device electrodes with polymeric binders leads to increases in specific capacitance of over 40% when compared to electrodes made with untreated few-layer graphenes. In addition, the values of specific capacitance that are achievable exceed those with activated charcoal electrodes with charcoals of much larger specific surface area.

202

The Grand Challenges for Carbon Fibre Composites

Fox, Bronwyn L1, Hameed, Nishar.


1 Manufacturing Futures Research Institute, Faculty of Science, Engineering and Technology, Swinburne University of Technology, PO Box 218, Hawthorn, Victoria,

Australia 3122 The global market for carbon reinforced composites is growing exponentially and is predicted to reach $38 billion by 2024 [1] with key applications in aerospace, automotive, defence, wind energy and civil engineering. This increase in demand has led to the development of higher volume production processes. Until recently, the rate limiting step was the epoxy resin cure cycle time, however, recent innovations in rapid cure epoxy materials have revolutionized the way we make advanced composite materials [2] with cure cycle times dramatically reduced from hours to minutes in the past two decades. If advanced automation in conjunction with rapid processing is utilised to manufacture complex high-volume parts at a rate of under 3 minutes, the current costs per part can be reduced from $50/lb down to $5/lb [3]. New digital approaches for manufacture of customized parts are emerging and by utilizing an Industry 4.0 approach, we can design and develop new smart composite structures in a cost effective and efficient way. Australia has a vibrant and growing manufacturing sector for carbon fibre composites, with the volume of carbon fibre consumed growing from 600 to 980 tons per year in the past 3 years. To ensure this capability flourishes, it is critical to build and secure an indigenous supply chain. The recent establishment of Carbon Nexus combined with CSIRO’s precursor facility is an important first step. This presentation will present a holistic view of the grand challenges for carbon fibre composites across the entire value chain with progress towards the solutions. (1) Market Report - Global Carbon Fiber Composite Market”, Acmite Market Intelligence 2016. (2) http://www.compositesworld.com/articles/automotive-composites-thermosets-for-the-fast-zone. (3) Mascarin et al., “Vehicle Light weighting”, U.S. Department of Energy Office of Nuclear Energy, 2015.

203

The peculiarities of dislocation behaviour in graphite

P. Mouratidis1, M. I. Heggie1, J. Kioseoglou2, M. Rayson3, and P. R. Briddon3

Presenting author’s e-mail: P. [email protected]

1 University of Loughborough, Loughborough, United Kingdom 2 Physics Department, Aristotle University of Thessaloniki, Thessaloniki, Greece

3 Newcastle University, Newcastle-upon-Tyne, United Kingdom

In the last decade the behaviour of dislocations in graphite has been examined theoretically, and the following conclusions were reached: (a) interlayer bonding occurs in the cores of prismatic dislocations, (b) basal dislocations have a Peierls stress of zero and hence move reversibly, (c) basal dislocation motion is inhibited by interactions with point defects, impurities or each other, and (d) where the interaction is strong it can give rise to buckling and folding of layers. The latter conclusion has recently been interpreted by others as a new defect called the ‘bulk ripplocation’. Here we present new Density Functional Theory calculations of basal dislocations in graphite using the AIMPRO code. They demonstrate conclusions above and draw out their role in deformation and radiation damage, including energy storage and changes in crystallite dimension. We focused on the dipole of basal dislocations in bilayer graphene. In order to introduce a pair of opposite sign on dislocations the displacement field predicted by elasticity theory is imposed on the perfect structure. The structural and electronic characteristics of the bilayer graphene as well as of the dipole of basal dislocations will be discussed in comparison with the well-established graphene structure.

204

The Road Ahead for Solar and Bioenergy Technologies

Martin Keller National Renewable Energy Laboratory

Every day, we face fluctuating oil and gasoline prices. We hear reports on the rising level of carbon dioxide in the atmosphere and its impact on the climate. And we see a growing world population with increasing needs for energy. Solar and bioenergy technologies are at the forefront of renewable, sustainable energy options that are meeting these needs now. Although renewable technologies have gained much greater levels of cost parity with fossil energy sources, continued innovation is necessary to meet global de-carbonization targets. Solar electricity can be generated by photovoltaic technologies. Scientific advances in this area continue to squeeze more power from the solar modules, but are also boosting efficiencies, reducing costs, and improving reliability of other photovoltaic devices such as thin films, multijunctions, and emerging technologies. In the area of solar fuels, research targets semiconductor devices that can efficiently and economically split water to produce hydrogen as an energy carrier. Bioenergy technologies include biological and chemical approaches to create solid, liquid, and gaseous fuels for electricity, transportation, and chemicals for industrial uses. Solid biomass can be combusted directly for heat and power. Various energy crops are used to produce a range of fuels. Significant new innovation in both solar and bioenergy area are pushing the boundaries for the science and deployment of renewables. This presentation will feature the latest scientific accomplishments and discuss the global imperative of continued investment in clean energy research.

205

Thermal stability improvement of amorphous silicon carbide fiber

Cho, K 1, Khishigbayar, K 1, Kim, K 1


1 Korea Institute of Ceramic Engineering and Technology, Jinju-si, South Korea

Low pressure curing method with iodine vapor was used on low softening temperature polycarbosilane (PCS) precursor for fabrication of continuous SiC fiber at relatively low temperature. The low curing temperature can provide with a wide range of PCS precursors, especially PCSs with low softening temperature, which have good spinning continuity, but many difficulties with conventional thermal oxidation curing method. The low pressure curing method under iodine vapor have shown the more positive effect on pyrolysis with early crystallization of β-SiC at 1300°C. Crystal size of β-SiC, cured at 0.008 kPa is around 2-3 nm larger than cured at 101 kPa. Therefore, the low pressure curing leads production and crystallization of β-SiC at a shorter period than required if cured at atmospheric pressure. In particular, the degree of C-H cleavage was higher at low pressure curing than the atmospheric pressure curing. In addition, the higher tensile strength of SiC fiber at elevated temperature can be obtained at 2.1 GPa with 0.008 kPa of curing pressure, compare to 1.3 GPa at 101 kPa of curing pressure condition.

206

Thermodynamic rationalization of graphitization: the critical temperature threshold

Ouzilleau, P.1, Gheribi, A. E.1, Chartrand, P.1.


1 Polytechnique Montreal, Montreal, Canada

Previous application of kinetic equations to model the effect of heat treatment temperature on the graphitization behaviour of carbon materials is well known. However, these studies could not explain apparently controversial experimental results, hindering conceptualization of key aspects of the graphitization mechanism. The present work focuses on developing a thermodynamic rationalization of the irreversible graphitization process based on the concept of a critical temperature at ~2550 K [1]. This thermodynamic model reflects how the concept of a critical temperature threshold for the surface energy of coke crystallites [2] (idealized, non-graphitic, graphitizable crystallites) constitutes the first step of the presently proposed graphitization scenario. The model is consistent with available graphitization experimental knowledge. This includes the experimental temperature threshold for the onset of true long range graphitic order, the apparent formation of linear carbon chains in graphitic carbons and the Oberlin polygonization temperature, all three phenomena apparently linked to a critical temperature of ~2550 K. Quantitative results for the validation of the model are given. Predictions for the average interlayer spacings (d002), the thermal diffusivities and the electrical resistivities as a function of graphitization temperature (between 2000 and 3300 K) of 51 graphitizable carbons (petroleum coke, polyvinyl chloride, anthracites, mesocarbon microbeads, polyimide films, etc.) are presented. Predictive accuracy is statistically evaluated. Near-ideal precision is obtained. The present graphitization rationalization provides a thermodynamic basis for future models focused on the graphitization mechanism. Finally, some comments on the preliminary modelling of the graphitizable/non-graphitizable character of carbons, based on the present thermodynamic principles, are discussed. [1] Ouzilleau et al., Carbon, 2016, 109, p.896 [2] Ouzilleau et al., Carbon, 2015, 85, p.99

207

Towards 3d Printing Devices for Energy Storage

Rocha, V.G1,2, García-Tuñón, E2, Markoulidis,F2, Feilden, E2, D’Elia, E2, Ni, N2, Shaffer,M2, Saiz,E2

[email protected]

1 Cardiff University, Cardiff, United Kingdom 2 Imperial College London, London, United Kingdom

Graphene, with its unique intrinsic properties, is the material expected to overcome the current limitations in a wide range of applications, from membranes and multifunctional composites to energy storage. However, this will only be possible through novel designs and approaches to integrate graphene in the fabrication of structures and devices combining multiple materials. In this respect, additive manufacturing (AM) is opening up multiple possibilities towards completely new and more efficient devices. Printing of graphene based aerogels has attracted huge attention. Different methods have been proposed but the challenge still remains to develop clean, simple and scalable approaches that will allow the fabrication of devices combining graphene with other materials. In this work we show a novel way to fabricate bespoke supercapacitor devices on demand that will be of interest to the wide cross-disciplinary scientific and engineering community. We describe how to prepare these graphene-based and metallic inks using a commercially available, low cost, water-based, thermo-responsive hydrogel (Pluronic F127). Using a robocaster with several printing nozzles we build components on-demand, combining inks with different compositions. As a proof of concept we make 3D supercapacitors, integrating the active material precursor (chemically modified graphene, CMG) and copper as the current collector. In this talk, I will present the processing approach, the behaviour of the inks and the properties of the devices.

208

Transverse Structure Control of Mesophase Pitch Based Carbon Fibrer

Sun, Z, Lu, Yonggen, Yang, C


Donghua University, Shanghai, China

Mesephase pitch based carbon fiber (MPCFs) usually crack due to radiation pattern on the transverse section. This work is aimed to alleviate this structure by doping polyacrylonitrile (PAN) into mesophase pitch. Carbon fibers were prepared through preheating, spinning and carbonization. It was found that very small amount of PAN not only alleviated the carbon fiber cracking by modifying the transverse structure but also took some co-carbonization effect for increasing the crystalline size. The transverse section of the MPCFs doped with 0.3 wt.% PAN transformed from radiation pattern into folded radiation pattern and the crack was suppressed effectively. Correspondingly, the crystalline length (La) and stacking height (Lc) increased and the tensile strength of carbon fibers was promoted.

209

Tunable surface chemistry of graphene oxides for controlled drug delivery

Liu, Z1, Li, Q1, Liu, J2, Barrow, C J1, Duan, W1, Yang, W1,*


1 Deakin University, Geelong, Australia 2 Qingdao University, Qingdao, China

Two-dimensional graphene oxide (GO) nanomaterials offer excellent loading capacities due to its rich surface functionalization by oxygen functional groups (Zhang 2010). Therefore, GO provides large surface area and vast functional groups for efficient drug loading, such as doxorubicin (DOX). These oxygen-containing groups considerably improve graphene’s water processibility and introduce chemical activity. So controllable tuning of GO surface chemistry is vital for a controlled drug delivery system (Liu 2015). Here we present a new method to controllably facilitate the DOX release from GO surface in vitro. First of all, we studied two promising interactions between GO and DOX, hydrogen bonding and π-π stacking interactions (Yang 2008). Strong evidences have been provided by UV-Vis, FTIR, Raman and fluorescence spectra to confirm both of these two interactions. Second, the loading conditions of DOX onto GO sheets were optimised considering the influence of pH, drug/carrier mass ratio and oxygen content of GO. Inspired by the result that GO has better loading capacity for DXR than its reduction products, we present a reductant-assisted DOX release in the mimicking of the physiological (pH 7.4) and cancer cell (pH 5.3) conditions. In this delivery system, we observed the introduction of L-ascrobic acid, which was used as the reductant of GO, is able to facilitate the drug release process, and the accelerated rate could be controlled by adjusting the dosages of L-ascrobic acid. Furthermore, the loaded DOX is much more stable on GO in neutral buffer than that in acidic buffer even with L-ascrobic acid, which agrees with its practical applications in real organisms.

210

Two-Dimensional Carbon-Encapsulated Fe3O4 Nanosheets Grown Via Oriented Attachment Mechanism

Jinyu Ning,1 Minhong Kong,1 Huaihe Song,1,2 and Jisheng Zhou1,2*

[email protected] (Zhou, J)


Technology, Beijing 100029, P. R. China 2 Changzhou Institute of Advanced Materials, Beijing University of Chemical Technology,

Jiangsu, P. R. China. Since the great progress in graphene, two-dimensional (2D) nanomaterials have been one of the most attractive research directions. But preparation of 2D nanosheets with nonlayered structure is still a big challenge in that there is a lack of an intrinsic driving force for their anisotropic growth. In this work, ultrathin 2D carbon-encapsulated Fe3O4 (Fe3O4@C) was prepared by an in situ co-pyrolysis method. The formation process of the ultrathin Fe3O4@C nanosheets (the thickness is ca. 5 nm) should be attributed to an Oriented Attachment (OA) mechanism. Different from the traditional crystal growth mechanism, Ostwald Ripening (OR), the OA mechanism leads to primary nanocrystals attaching together and forming larger particles very quickly. Primary Fe3O4@C nanocrystals quickly attached to each other and they turn into small Fe3O4@C nanosheets with adjusting their orientation to decrease the surface free energy. Therefore, diverse anisotropic ultrathin Fe3O4@C have been created. When used as anode materials for lithium-ion batteries (LIBs), the Fe3O4@C nanosheets demonstrated perfect cycling stability and rate-performance. Good electrochemical performance of the ultrathin Fe3O4@C nanosheets should be attributed to its ultrathin carbon coated 2D nanostructures.

211

Utilizing Supercritical Extraction for Kinetic Modeling of Pyrene Pitch Formation.

Hoffman W 1 , Lamie C 2 , Bruce D 2 , Thies M 2


Affiliations 1 Edwards Air Force Base, Edwards AFB California, United States

2 Clemson University, Clemson South Carolina, United States

Facilitated by supercritical extraction (SCE), the kinetics of oligomer formation in pyrene pitches has been studied. The starting model pitch samples were produced by the catalytic polymerization of pure pyrene using AlCl3 at temperatures from 300-500°C. Each sample was reacted for 1, 4, 8, and 24 hours in order to vary the oligomeric composition of the final pitch product. Using supercritical toluene, the samples then were fractionated into their monomer, dimer, trimer, and higher oligomer constituents in order to determine the concentration of each. Fraction purity was confirmed using MALDI-TOF and DEPT-135 C13-NMR. Using this information, we were able to propose a model for the formation of the pyrene pitch, along with kinetic constants to fit the concentration profiles obtained. To supplement this study, experiments were done to determine the activation energies of the reactions taking place. This was done by determining the oligomeric composition of pyrene pitches reacted at varying temperatures, and then fitting them to an Arrhenius model. Using the activation energies, we can determine if the reactions are ones that are diffusion controlled or kinetically controlled.

212

VORTEX FLUIDICS MANIPULATION OF NANOCARBON

Vimalanathan, K. and Raston, C.L.


Flinders Centre for NanoScale Science & Technology, School of Chemical & Physical Sciences, Flinders University, Adelaide SA 5001, Australia

Carbon nanomaterials of various dimensionalities have gained a unique place in nanotechnology owing to their explicit physical and chemical properties for a myriad of applications. Exquisite control over their morphology, shapes and size is pivotal to harness their full potential. This research focuses on employing the use of process intensification as an alternative strategy towards the fabrication and manipulation of novel forms of carbon material under continuous flow at the nanoscale level. The synthesis of nanocarbon potentially benefits from innovation in using novel energy efficient processing platform, the most recently developed microfluidic platform, the vortex fluidic device (VFD). The VFD has a number of novel and facile capabilities including but not limited to controlling self assembly processes, and the fabrication and growth of carbon nanomaterials with distinct control over the morphology, shape and size of the nanostructures. Examples include slicing carbon nanotubes in a controlled way while irradiated with a pulsed laser operating at 1064 nm wavelength, as a process incorporating green chemistry metrics, including scalability.1 In addition, the VFD is effective in fabricating toroidal arrays of single walled carbon nanotubes,2 the formation of self assembled arrays of fullerene C60 in the form of nanotubules which are superior sensing material for detecting small molecules,3 and the direct exfoliation of graphene into graphene scrolls. Employing the use of controllable mechanoenergy generated in the VFD allows access to new forms of nanocarbon material with scalability incorporated at the inception of science. This approach attempts to ensure environmental and economical feasibility while offering potential for uptake in industry. 1. K. Vimalanathan, J. R. Gascooke, I.S. Martinez, N.A. Marks, H. Kumari, C.J. Garvey, J.L. Atwood, W.D. Lawrance, C.L. Raston. Scientific Reports, 2016, 6, 22865. 2. K. Vimalanathan, X. Chen, C.L. Raston. Chemical Communications, 2014, 50, 11295-11298. 3. K. Vimalanathan, R.G. Shrestha, Z. Zhang, J. Zou, T. Nakayama, C.L. Raston. Angie Wandte Chemie, 2016, 55.

213

Water desalination with graphene oxide/graphene based membranes

Morelos-Gomez, A1, Cruz-Silva,R.1,2, Muramatsu, H.2, Ortiz-Medina,J.1, Araki,T.1,3, Fukuyo, T.4, Tejima, S.1,3, Takeuchi,K.1, Hayashi, T.2, Terrones, M.2,5, Endo, M.1

[email protected]

1 Global Aqua Innovation Center, Shinshu University, Nagano, Japan 2 Institute of Carbon Science and Technology, Shinshu University, Nagano, Japan

3 Research Organization for Information Science & Technology, Tokyo, Japan 4 Showa Denko K.K., Institute for Advanced and Core Technology, Chiba, Japan

5 Department of Materials Science and Engineering, Department of Chemistry, and Department of Physics, The Pennsylvania State University, Pennsylvania, USA

The demand of water resources is increasing every year, pushing the development of technologies to meet the growing water consumption. In this regard nanofiltration, reverse osmosis and forward osmosis membranes are being used and the majority of them are made entirely by polymers. However, these polymers could suffer poor chemical resistance and membrane fouling, therefore a different material as the active layer is needed. Graphene oxide (GO) membranes are promising for water treatment due to its chemical stability and antibioufouling properties. However, the majority of reported results only work in dead end flow systems due to the low water shear stability of GO. In this work, an active layer composed of GO, few-layer-graphene (FLG) and deoxycholate was developed with an easy spray deposition method on top of a porous support, where an intermediate adhesive layer was used between the GO layer and the support. The content of GO was varied and an optimal condition was found for the highest NaCl rejection (c.a. 90%) from a water feed of 0.2% by wt. NaCl solution. The obtained values are much higher than others reported using GO based membranes (≤ 40% NaCl rejection).[1,2] The membranes exhibited good stability against water shear from the used cross-flow equipment for desalination. In addition, the membrane could separate a mixture of anionic and cationic dyes favouring the permeation of cationic dyes. It is among the first GO membranes to be operated in day timescales in a cross-flow system with good water shear stability. Therefore, opening possibilities for real world applications of GO membranes. References 1. Y. Han, et al., Adv. Funct. Mater. 23, 3693 (2013). 2. M. Hu, B. Mi, Environ. Sci. Technol. 47, 3715 (2013).

214

Element Silicon in Carbon Fibers Under High Temperature Treatment

Hao, WZ, Zhang, XJ, Tian, YH, Xu ZS

Presenting author’s e-mail: [email protected],cn

Beijing University of Chemical Technology, Beijing, China

This presentation mainly discussed the presence of silicon in domestic PAN-based carbon fibers, as well as the changes of it in carbon fibers treated with different temperatures. The contents of silicon are greatly correlated to heat-treatment temperature. X-ray photoelectron spectroscopy (XPS), inductively coupled plasma atomic emission spectrometry (ICP) and organic element analysis were used to characterize the changes. The results show that carbon content increases with the increase of heat-treatment temperature, while the content of silicon decrease. The atoms of silicon in carbon fiber are in the forms of Si-O2 (banding energy 103.4eV), Si-O (banding energy 102.6eV) and Si-N(banding energy 102.0eV).

215

Improving thermal-shock resistance of SiC-coated C/Cs with ferrocene refined SiC

Huo C., Guo L., Li H., Wang C., Zhang Y.



To improve the thermal shock resistance of SiC coatings applied on carbon/carbon (C/C) composites, ferrocene ((C5H5)2Fe) was introduced in the coatings during the pack cementation process. The microstructure and thermal shock resistance of modified SiC coating were studied. The HNO3 treated carbon fiber and the introduction of (C5H5)2Fe could raise the nucleation point and the decomposition of (C5H5)2Fe can slow down the sintering process, which helps to decreased the sizes of SiC particles and micro-defects (including micro-cracks and micro-holes) and resulted in a relatively dense structure. Thermal shock test revealed that the mass change rate of C/C composites decreased from 18.25% to 10.08% after thermal cycle test between 1773 K and room temperature for 25 times, suggesting a better shock resistance for the modified SiC coating compared with the base coatings (without modification). This work provides a novel way to modify the SiC coating capable of releasing the thermal residual stress and decreasing the oxygen diffusion channels and then further increasing the thermal shock resistance of C/C composites without other supplementary protective coatings.

216

Self-healing YSZ-La-Mo-Si heterogeneous coating fabricated by plasma spraying to protect carbon/carbon composites from oxidation

Wang, C.C.1, Li, K.Z.1, Shi, X.H.1,

Author’s e-mail: [email protected], [email protected], [email protected];

1Northwestern Polytechnical University, Xi’an, China

To protect carbon/carbon (C/C) composites against oxidation, YSZ-La-Mo-Si (YSZ-LMS) heterogeneous coating was prepared by the plasma spraying using YSZ (Y2O3-stabilized ZrO2), MoSi2 and LaB6 as raw materials. The thermogravimetric and isothermal oxidation results indicated that the as-prepared coating reveal superior oxidation protective ability at elevated temperatures, which protected the C/C composites from oxidation for 50 h at 1773 K with a mass loss of 0.58 % (1.31 mg·cm-2). The generation of SiO2, ZrSiO4, Y2SiO5 and La2O3 expanded the volume of solid phase and decreased the volatilization of SiO2 to form a denser Zr-Y-La-Si-O oxide glass layer. Among them, the volume expansion promoted the formation of compressive stress within the coating at this high temperature. These compressive stresses restrain the initiation and propagation of cracks and boost the oxidation protection of the coating for C/C composites. The corresponding high temperature oxidation activation energy of the coated C/C composites at 1573-1773 K is calculated to be 74.466 kJ/mol.

217

2-D porous Co3O4 nanosheets via graphene mimicking

Park, H, Noh, SH, Han, TH


Hanyang University, Seoul, Republic of Korea In this presentation, graphene mimicking for the preparation of a new type of 2D oxide nanosheets is introduced. 2D nanoscale oxides have attracted a large amount of research interest due to their unique properties. We report a straightforward synthetic approach to prepare 2D porous Co3O4 nanosheets using graphene oxide (GO) as a sacrificial template. By taking advantages of the catalytic ability of Co3O4 to degrade carbon backbones, as well as the thermal instability of graphene, porous 2D Co3O4 nanosheets consisting of Co3O4 nanocrystals (ranging about 10 to 20 nm in diameter) were successfully synthesized without the loss of the 2D nature of GO. Our 2D porous Co3O4 nanosheets as a lithium storage material exhibited a high reversible capacity of 1279.0 mAh g-1 even after 50 cycles. This is vastly superior to the theoretical capacity of Co3O4 based on the conversion mechanism from Co3O4 to Li2O and metallic Co. The extraordinary capacity of our 2D porous Co3O4 nanosheets may come from the peculiar 2D nanostructure and high pore volume, which promote a reversible electrochemical reaction. These reactions may include the conversion reaction between Co3O4 with lithium and the reversible formation of an organic SEI layer on the surface of the Co3O4 nanosheets.

218

A cooperative interface for highly efficient lithium–sulfur batteries

Huang, JQ1,2, Peng, HJ2, Zhang, ZW2, Zhang, Q2




Lithium–sulfur (Li–S) battery is a promising substitute to the current lithium-ion

battery technology, as theoretically, it offers the highest specific energy of 2600 Wh kg−1 among solid-state batteries. However, several technical challenges, such as the low utilization of sulfur, poor cycling life, low efficiency, and severe self-discharge, are strongly associated with the insulating nature of sulfur compounds and the well-known “shuttle” of soluble polysulfide intermediates, requesting effective scientific solutions toward commercially viable Li–S batteries.

We proposed a unique strategy by building a cooperative interface between the S cathode and separator to suppress the polysulfide shuttle and enhance the reaction kinetics. Nano-sized “sulfiphilic” LDHs and mesoporous “lithiophilic” NG were assembled rationally with cooperation in providing bifunctional chemical *Li and *S binding, enhancing the retention of polysulfides, and catalyzing the formation of Li2S. The Li–S batteries employing LDH@NG separators exhibited high capacity, outstanding rate capability, long lifespan, and stable operation of high-loading S cathode and Li anode. This open ups the rational design of advanced materials with cooperative interfaces toward effective regulation of active intermediates.

Therefore, the high-energy-density energy storage devices with multi-electron chemistries and multiphase conversion can be further understood through the energy chemistry of cooperative interfaces. The concept of cooperative interfaces is expected to be further extended to other hybrids with two building blocks having unexpected properties for unique applications. [1] Peng, H. J.; Zhang, Z. W.; Huang, J. Q.; Zhang, G.; Xie, J.; Xu, W. T.; Shi, J. L.; Chen,

X.; Cheng, X. B.; Zhang, Q. A Cooperative Interface for Highly Efficient Lithium–Sulfur Batteries. Adv. Mater. 2016, 28, 9551-9558.

219

Activated Carbon Impregnated with Zirconium Hydroxide as the Sorbent for Toxic Gases

Li Li1, 2, Li Kai1, 2, Ma Lan1, Wang Xinbo1, Luan Zhiqiang1, 2

[email protected] 1Research Institute of Chemical Defense, China

2 State Key Laboratory of NBC Protection for Civilian, China

Using zirconium sulfate and copper carbonate as reactants, two preparation methods have been investigated for impregnating zirconium hydroxide and copper in the activated carbon. The objective of this effort is to evaluate the balanced filtration activity for CBRN by contrasting two preparation methods. The characterizations of the impregnated carbons are analyzed by Nitrogen Adsorption, X-ray Diffraction (XRD) and Scanning electron microscope (SEM) experiments. And the samples are assessed for the adsorptions abilities to remove chemically diverse toxic gases, namely CNCl, SO2 and C6H6 from steams of air in respirator applications.

The structure and surface analysis show that zirconium hydroxide prior to generate in the porosity of activated carbon, which are tiny and uniform. And the impregnated copper is presented as copper oxide phase. Comparing to the impregnated carbon which is prepared by co-impregnation method, the impregnated carbon which is prepared by separate-step impregnation method can obtain more expected active components and display more comprehensive balanced capacity for the removal of acidic and organic toxic chemical. And the addition of copper oxide to the activated carbon impregnated with zirconium hydroxide can elongate the service time for CNCl and SO2 filtration by promoting catalytic hydrolysis and providing a sink for oxidation products.

220

Activated Carbon-Incorporated Cigarette Filter For Tar and Nicotine Removal

Kong-gij, B., Kunapisitkul, S., Wadsungnoen, P., Boonyoung, P., Treeweranuwat, P., Nueangnoraj, K.


School of Bio-Chemical Engineering and Technology, Sirindhorn International Institute of Technology, Thammasat University; Thailand

Cigarette smoke is one of the world environmental issue, causing several health problems to both of the smokers and non-smokers. Tar and nicotine are the most important matters in the smoke, which directly affects the respiratory system, such as lung cancer and emphysema. Adding a filter into the cigarette can partly screen out such the harmful substances. Additives, such as zeolites and activated carbon can be added into the filter to improve the adsorption ability. However, not only the high specific surface area, which lead to the enhancement of physisorption, the surface chemistry of solid additive is also important to employ the chemisorption. This work aims to develop the activated carbon that can effectively remove tar and nicotine from the cigarette mainstream smoke. Activated carbon was derived from hemp (Cannabis sativa), using chemical activation with phosphoric acid. Process parameters such as activation temperature and impregnation ratio will be investigated. The resultant activated carbons will be fully characterized to understand the effect of pore structure and surface chemistry of the carbons on the adsorption ability of tar and nicotine from cigarette mainstream smok

221

Activated Polymer of Intrinsic Microporosity as Anode Materials for Lithium-Ion-Supercapacitor

Yang, M1, Meng QH1, Cao B1, Yu YH1


1 College of Materials Science and Engineering, Beijing University of Chemical

Technology, Beijing, China With the rapid development of sustainable energy, the demand for high-performance electrochemical energy storage services to make efficient use of energy has significantly increased. Lithium-ion supercapacitor (LIC), a novel hybrid energy storage service with high energy density, excellent power capability and long cycle life, has emerged in 2001 by Amatucci to meet this demand. Polymer of intrinsic microporosity (PIM) with a high fractional free-volume (26%) and high surface area of 760 m2 g-1 is a hopeful role for anode materials for LIC。In this paper, PIM-1 which was activated by CO2 was used to be the anode material for LIC. The structure, morphology, and pore-size distribution of PIM was characterized by SEM, FTIR, and BET methods. And the electrochemical properties of PIM were studied by the galvanostatic charge and discharge test. The results show that the discharge specific capacity of PIM, when it was carbonized at 800 , was 268.4 mAh g-1 at a current density of 0.1 A g−1 and 124.4 mAhg-1 at a higher current density of 2A g−1. However, when it was activated at 1000 , the discharge specific capacity of PIM was 1125.9 mAh g-1 and 415.6mAh g-1 at the current of 0.1A g−1 and 2 A g−1. The results indicated that CO2 activation effectively modified the porous structure of PIM and improved its specific surface area to achieve better porosity, thereby enhancing the electrochemical properties.

222

Activation Studiy Of Carbon Chars Derived from High Temperature Pyrolysis of Cellulosic Biomass

Gallego, N. C.1, Biss, B.2, and Evans, N.2 and Contescu, C. I1


1 Oak National Laboratory, Oak Ridge, Tennessee, USA

2 formerly with Proton Power, inc., Lenoir City, Tennessee, USA

High temperature pyrolysis of cellulosic biomass is an inexpensive way for production of hydrogen or synthetic fuels which are economically competitive with fossil fuels. The process also generates significant amounts of char. In search for finding value-added use of this by-product, the chars obtained from various sources were assessed for their potential of being used as feedstock for physically activated carbons. The results showed that the charred materials obtained at high temperature have already incipient porosity and NET surface areas in the range of 150 – 300 m2/g, depending on the biomass source. A thermogravimetric study of oxidation by CO2 was performed to determine the effect of temperature on the oxidation rates and the apparent activation energy. These parameters helped to select physical activation conditions for targeted weigh loss levels between 30 and 40 %. The characterization of activated carbons by gas adsorption methods showed differences in the properties (total pore volume and pore size distribution, BET surface area) that could be traced back to the nature of the original biomaterial type (e.g. soft/hard wood, grassy feedstock etc). With proper selection of the raw material and physical activation conditions it was possible to obtain activated carbons with surface area in the range of 800 – 1100 m2/g, total pore volumes of 1.1 – 1.4 cm3/g, and adjustable micropores:mesopores ratios in the range of 3:1 to 1:3. These properties are similar to those of many commercially available activated carbons used for treatment of municipal water or for removing heavy metals from various water streams in industrial processes. This work was supported by the State of Tennessee and the University of Tennessee through the RevV! Manufacturing Voucher Program.

223

Adsorption and Thermal Desorption of Siloxanes for the Purification of Biogases

Giraudet, S1, da Silva Santos, R1, Le Cloirec, P1

[email protected]


The siloxanes are characterized by the bond between the atom of silicon and oxygen. When the siloxanes are submitted to high temperatures, they oxidize, decompose and form a silica deposit. This deposit impedes the energy production from biogases. Removing siloxanes during the production of the biogas is then a requirement. Adsorption by activated carbons was studied to assess the performance of this treatment and the thermal desorption was studied for a possible regeneration of the adsorbents. First, adsorption kinetics and isotherms of adsorption were determined. Four types of activated carbons were chosen: Pica B1 and NC60 (granular activated carbons) and CCI FM30K and Dacarb THC515 (activated carbon fiber cloths). On the other hand, two siloxanes were selected: siloxanes D4 and L3, to represent linear and cyclic siloxanes. Generally, the activated carbon B1 (produced from wood, with the largest mesoporous volume) had the highest efficiency, in comparison to the other adsorbents. However, surprisingly, during the adsorption, degradation by-products were observed and identified. The Siloxane L3 decomposed into two siloxanes: Siloxane L2 and octamethyltrisiloxane. The IAST was used to determine the amount of each compound adsorbed and to estimate the reaction rate. However, the cyclic siloxane D4 didn’t decompose. Concerning the thermal desorption, the temperature of desorption as well as the amount of siloxanes desorbed were dependent on the type of activated carbon. In the case of siloxanes D4, a maximum of 15 wt% was desorbed up to 400 °C, which meant that higher temperatures would be required to achieve complete regeneration.

224

Adsorption Property of Activated Carbon containing Nitrogen in Liquid Phase

Naoaki Kusaka, Jun’ichi Hayashi, Isao Hasegawa Department of Chemical, Energy and Environmental Engineering, Kansai University, 3-3-

35 Yamate-cho, Suita, Osaka, 564-8680, Japan E-mail: [email protected]

Activated carbons are very versatile adsorbent due to their high surface area and well developed pore structure. Recently, the studies of adsorption property by using activated carbons containing nitrogen have been actively conducted. And it has been reported that the amount of adsorbed water vapor on the activated carbon containing nitrogen increases in the range of low relative pressure. The nitrogen functional groups containing nitrogen enhance the polarity of the surface of the activated carbon. Therefore, the activated carbon containing nitrogen effectively adsorbs hydrophilic adsorbate. In gas phase adsorption, the adsorption property of the activated carbon containing nitrogen has been studied ambitiously. However, in liquid phase adsorption, there are not so many studies. Therefore, in this study, the adsorption property of the activated carbon containing nitrogen was examined in liquid phase adsorption and the influences of the polarity of the solvent and the adsorbate on the adsorption property were investigated. The activated carbon containing nitrogen was prepared from the sludge by chemical activation with ZnCl2. Phenol was employed as the adsorbate, and water and cyclohexane were used as the solvent. It was found that amount of adsorbed phenol in cyclohexane solution was promoted than that of aqueous solution. Moreover, it was found that though the nitrogen contents in the activated carbon increased, the amount of adsorbed phenol was not influenced.

225

Structural Relationship on Anodic Performance of Biomass-Derived Hard Carbons for Nib

Chung D1, Han Y1,2, Nakabayashi K1,3, Miyawaki J1,3, Yoon SH1,3


1 Interdisciplinary Graduate School of Engineering, Kyushu University, Fukuoka, Japan

2 Division of Green Chemistry & Engineering Research (KRICT), Daejeon, Korea 3 Institute for Materials Chemistry and Engineering, Kyushu University,

Fukuoka, Japan

Na-ion batteries (NIBs) are expected to be an alternative to lithium-ion batteries for the low cost and large scale energy storage system in the near future. In NIB system, Na ions cannot be intercalated and de-intercalated into/from the graphite anode upon its charging/discharging like LIB. Therefore, the development of suitable anode materials is the critical issue for a successful commercialization of NIBs. Recently, a variety of researches has been progressed to find out the suitable materials for NIBs. Among many candidates, hard carbon is expected to be the most promising one as anode material in NIBs due to the low cost in production, easy obtainability as renewable resource and non-toxicity in the heat treatment. In this study, we developed effective anodes for NIBs and closely examined their structural effects on the electrochemical performance of biomass-derived hard carbons using two different biomasses which were Indonesian mangrove and Ethiopian eucalyptus. Among them, hard carbon prepared from Ethiopian eucalyptus char exhibited remarkably high first-cycle Coulombic efficiency which was 87.7%.

226

Anti-Icing Coating Based on a Mixture of Nanotubes and Nanofibres

Lesbayev, B1,3*, Prikhodko, N1,2, Nazhipkyzy, M1,3, Nurgozhina, D1, Ustaeva, G1, Temirgaliyeva, T1,3, Elemesova, J1,3, Mansurov, Z1,3


1Institute of Combustion Problems, Almaty, Kazakhstan 2Almaty University of Energetics and Communications, Almaty, Kazakhstan

3Al-Farabi Kazakh National University, Almaty, Kazakhstan

The researchers are interested in developing methods for creating anti-icing coating based on carbon nanomaterials having superhydrophobic properties. In this paper we developed a method of synthesizing the CVD method a nanostructured hydrophobic material consisting of a mixture of carbon nanotubes and nanofibers on the surface of the mineral shungite produced on an industrial scale in Kazakhstan under the brand name "Taurit". Mineral shungite under the trademark "Taurit" is a powder having an average particle size of 20 microns, contains 75% Si02 and 15% carbon. Preliminarily the shungit impregnated with a solution of nickel nitrate. As an precursor for the synthesis of carbon nanotubes and nanofibers was used the propane-butane mixture. By heating in an an argon atmosphere to a temperature of 650 ºC for 30 min was performed reduction process metallic nickel nanoparticles out nickel nitrate by reaction with particulate carbon, which is contained in shungite. The synthesis process was performed at temperatures of 700-800 °C under an argon flow rate of 80 cm3/min and propane-butane mixture of 80-100 cm3/min. With the use of the resulting mixture of carbon nanotubes and nanofibres, using polyurethane glue as a binder, the authors designed and created a composite material having the property anti-icing. With the use of physico-chemical methods was to study the structural characteristics and properties of the anti-icing coating. Were conducted laboratory the testing process of freezing water droplets on the surface of the obtained anti-icing coating, when tilted more than 35° is absent formation an ice crust.

227

Application of Natural Carbon Fiber for Oil Spill Sorption

Eiad-ua, A1, Gunpum, W1, Viriya-empikul, N2, Faungnawakij, K3


1 King Mongkut’s Institute of Technology Ladkrabang, Bangkok, Thailand 2 King Mongkut’s University of Technology Thonburi, Bangkok, Thailand

3 National Science and Technology Development Agency, Pathumthani, Thailand Oil spill can be cleaned up using several techniques. Natural sorbents are proper choices due to their availability, sustainable, eco-friendly and low cost. Carbon fiber from biomass was used for oil sorption. In this study, carbon fiber have been successfully synthesized from cattail flower via hydrothermal process for removing oil spills from water. This research investigates the effect of hydrothermal temperature (140-220oC) and hydrothermal time (2-24 h) as sorbent materials of used motor oil, crude oil and slop oil, respectively. The results indicated that hydrothermal process at 180oC for 8 h had a highest oil sorption capacity compared to the others. The results showed that the maximum adsorption capacity of carbon fiber and used motor oil, crude oil and slop oil were about 18.93, 15.76 and 12.54 gram of oil adsorbed per gram of sorbent respectively. Their recycling performance was excellent as they can be used for ten times until they reach 50% of the sorption capacity of the 1st cycle. In addition, carbon fiber was close to superhydrophobic (contact angle 149o) and did not adsorb any water during oil spill clean up.

228

Application of Soot as a Composite Material For Li/S Battery Electrodes

Temirgaliyeva, T.S1,2, Nazhipkyzy, M1,2, Nurgain, A1.2, Lesbayev, B.T1.2, Prikhodko, N.G1, Mansurov, Z.A1,2

[email protected]

1Institute of Combustion Problems, The laboratory “Synthesis of carbon nanomaterials in

flame”, Almaty, The Republic of Kazakhstan 2Al-Farabi Kazakh National University, Faculty of chemistry and chemical technology,

Department of chemical physics and material science, Almaty, The Republic of Kazakhstan

Preparation of carbon nanomaterials is an important field. We synthesize soot through

the combustion of propane-butane mixture on surfaces. Hydrophobicity is characterized through the contact angle for water droplets placed on a surface covered with this soot. The influences of an electric field and metal catalysts are examined. Samples of soot obtained by burning propane-butane mixture with an imposed electric field of negative polarity show that the soot has a high dispersion and structural ordering, which enhances its hydrophobicity. The morphology structure of synthesized materials were investigated by scanning electron microscope.

Although sulfur is considered one of the promising candidate materials for the next generation lithium-ion batteries, lithium/sulfur (Li/S) batteries, because of its high theoretical gravimetric capacity, 1672 mAh/g and its extremely low cost, USD 150/ton (LiCoO2 typically costs USD 40/kg), there are several challenging issues in order to realize Li/S batteries. Many efforts have been dedicated to impregnating sulfur, in Li/S batteries, into various carbon matrixes as mesoporous carbons, carbon fiber, carbon nanotubes, graphene.

In this work, we have been developed the simple method of synthesize sulfur/soot/polyacrylonitrile composite. Sulfur/soot/polyacrylonitrile composite was synthesized by heat treatment at 300 0C for 3 h in inert atmosphere. Integration of soot in the composite results highly conductive and highly conductive and mechanically flexible framework with enhanced electronic conductivity and ability to absorb the polysulfides into its structure. The cell with this S/SOOT/PAN composite cathode demonstrates a stable reversible specific discharge capacity of 800 mAh g-1 after 50 cycles at 0,1 C.

229

Arsenic(V) Electroadsortion: Effect of Surface Chemistry and Porosity of Activated Carbon Electrodes

Chazaro-Ruiz, L1, Santoyo-Cisneros, R1, Rangel-Méndez, R1

[email protected] 1División de Ciencias Ambientales, Instituto Potosino de Investigación Científica y

Tecnológica IPICYT, San Luis Potosí, S.L.P., Mexico

The presence of arsenic in natural waters is a global problem, due to its toxic effects; it has been classified as a priority pollutant in different countries. Typical chronic effects of arsenic exposure include skin diseases as well as cardiovascular, neurological, renal and respiratory disorders. The elimination of arsenic from water has attracted much attention from the scientific community allowing the development of technologies to remove arsenic from water. In spite of their simplicity, the adsorption methods are generally inefficient in reducing the arsenic concentration to acceptable levels (below 10 ppb) in drinking water, since they require highly operational conditions such as pH and temperature control, low selectivity, regeneration capacity, etc. This problem has prompted research into alternative treatments that can be used for the removal of arsenic at low concentrations. An example of such processes is the separation technologies driven by the action of an electric field, such as electroadsorption. The yield in the electro-adsorption process is strongly dependent on the physical and chemical properties of the electrode materials, including, pore arrangement, specific surface area, and pore size distribution. It is well known that carbon materials have preferable characteristics such as high surface area and high conductivity. In this work we will present an study of the influence of the electrical conductivity, specific surface area, surface charge and particle size of a commercial granular activated carbon on the electroadsorption of As(V). Also the effect of the presence of anions (F, Cl, SO4

2-, NO3,

PO43) in a competitive environment.

.

230

Atom-Functionalized Carbon-based Nanomaterials in Energy Applications

Ting Liao School of Chemistry, Physics and Mechanical Engineering, Queensland University of

Technology, QLD 4000, Australia [email protected]

Inexpensive, metal-free materials of high performance in energy application as diverse as catalyst, supercapacitors, and electronic devices, is highly desirable to replace currently widely used metal or metal oxides. Modification of carbon-based nanomaterials by the introduction of appropriate elements or functional groups or nanosized particles may enable the manipulation of electronic, structural, and chemical properties that allows targeting of superior performance. In this presentation, a strong facilitating effect of heteroatom doping or welding graphene nanoribbons has been illustrated by DFT calculations, which includes stimulating sensing and dissociation of molecules, charge carrier adsorption and transfer in an aqueous environment, and change to the hydrogen evolution reaction with the presence of semiconducting nanoparticles. The calculated results not only confirm the possibility of manipulating the performance of carbon-based electronic, optical and electrochemical devices in energy application through chemical functionalization but, more importantly, provides the physical rationale for further design strategies

231

Batteries marry air pollutants: recover H2S in Li-S battery

Liu, D H 1, Zhang, C 2,*, Zhi, L J3, Yang, Q H1,4,5,*


1 School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300350, China

2 School of Marine Science and Technology, Tianjin University, Tianjin, 300072, China 3 National Center for Nanoscience and Technology, Beijing, 100150, China

4 Graduate School at Shenzhen, Tsinghua University, Shenzhen, 518055, China 5Tsinghua-Berkeley Shenzhen Institute (TBSI), Tsinghua University, Shenzhen, 518055,

China Air pollution has a negative impact on the human health and quality of life, and

environmental protection combined with advanced clean energy techniques are hot spot for the whole world. The conversion of air pollutants into high performance electrode for energy storage devices is a promising solution. In this talk, we will present our recent work on the combination of air pollutant control with advanced Li-S battery: 1) H2S was demonstrated as a highly-effective reducing agent for graphene oxide (GO), and a S/rGO composite was simultaneously prepared by the reaction between H2S and GO, which shows great potential as cathode material for Li-S battery. 2) A high-density S/graphene monolith was prepared by optimizing the interaction between H2S and GO, and a high volumetric capacity was delivered by this unique composite with abundant “ink-bottle like” meso-pores. 3) Highly-dispersible sulfur nanoparticles (HDS) with controllable size were successfully prepared for high performance Li-S battery. For example, a HDS/carbon nanotube composite can deliver the theoretical capacity of sulfur at 0.5 A g-1, and even at a high current density of 5.0 A g-1, a capacity of ~750 mAh g-1 can be retained. Therefore, this approach is expected to control heavy air pollutions, and more importantly, to recover the sulfur converted from heavy air pollutants in a new energy technology.

References: 1. C. Zhang, Q.-H. Yang*, et al. Reduction of Graphene Oxide by Hydrogen Sulfide: A Promising Strategy for Pollutant Control and as an Electrode for Li-S Batteries. Adv. Energy. Mater., 2014, 4, 1301565. 2. C. Zhang, D.-H. Liu, Q.-H. Yang*, et al. A high-density graphene–sulfur assembly: a promising cathode for compact Li–S batteries. Nanoscale, 2015, 7, 5592. 3. C. Zhang, D.-H. Liu, Q.-H. Yang*, et al. Conversion of air pollutants into high performance S cathode in Li-S batteries. Submitted.

232

Biomass-Based Three-Dimensional Network of Carbon Nanosheets For Lithium-Ion Battery Anodes

Guo S1, Chen Y1, Chen X1, Zhou J1, Ma Z1, Song H1*

[email protected]

1State Key Laboratory of Chemical Resource Engineering, Beijing Key Laboratory of

Electrochemical Process and Technology for Materials, Beijing University of Chemical Technology, Beijing 100029, P. R. China

*[email protected]

A simple synthesis strategy for fabricating biomass-based three-dimensional network of nitrogen-doped (N-doped) carbon ultrathin nanosheets (N-CNS) using soybean milk as the carbon precursor and sodium chloride as the template was reported in this research. The synthesis procedure of using biomass to fabricate carbon materials is low cost, environmental friendly and easy to control compared with the traditional synthesis methods. When the N-CNS was further used as the anode materials for lithium ion batteries, it exhibits good rate performance (1212, 902, 708, 555, 420 and 336 mAh g-1 at 0.05, 0.1, 0.2, 0.5, 1, and 2 A g-1, respectively) and superior cycling performance at a high rate (355 mAh g-1 at 1 A g-1 after 500 charge-discharge cycles). The excellent electrochemical performance may be attributed to the unique 3D integrative features and heteroatom composition. Furthermore, this study demonstrates the wide prospects of exploitation of biomass as a potential anode for the energy storage application.

233

Brownian Dynamics of CNT Aerogel Formation

Hoecker, C1, Bhalerao, A1, de la Verpilliere, J1, Graves, B1 and Boies, A1


1 University of Cambridge, Cambridge, United Kingdom

The aggregation of spherical particles in (dense) particulate systems is well studied. While it has been shown that for certain conditions an aerosol of spherical primary particles can form a macro structure, i.e. gel, little is known about the agglomeration of 1-D carbon nanotube (CNT) materials. To understand the gelation phenomenon it is useful to look at the kinetics of cluster aggregation which can be determined by means of Brownian Dynamic Simulation. In this poster we present our results on adopting existing aggregation and gelation theories and modifying them to describe the aggregation in CNT aerosols which eventually leads to an aerogel formed of CNTs within CNT reactors. These findings can then for example be related to the continuous gas phase process for the bulk production of CNTs, to identify important process parameters. We will describe the aggregation in a CNT aerosol by assuming that the CNT growth takes longer than the CNT agglomeration and that agglomeration is therefore the dominant mechanism:

.

Parameters like a CNT diffusion coefficient, a rotational diffusion coefficient of CNTs and a CNT collision kernel will be defined. A characteristic CNT rotation time as a function of CNT length and diameter can be derived as:

These models result in collision kernels of CNTs which are useful for continuum-scale modelling of the CNT reactors.

234

Capacitive performance of hierarchical porous carbons derived from lightweight cork (Quercus Suber)

Ugbo, F 1, Dangbegnon, J1, Bello, A1, Khaleed, A1, Barzegar, F1, Oyedotun, K1, Madito, J1,

Olaniyan, O1, Manyala, N1

[email protected] 1Department of Physics, Instititute of Applied Materials, SARChi Chair in Carbon Technology and Materials , University of Pretoria, Pretoria 0028, South Africa. Activated carbon (AC) derived from biomass lightweight cork (Quercus Suber) material is synthesized by KOH activation with different mass ratios of Quercus Suber: KOH in order to investigate the electrochemical properties of the AC produced in relation to KOH concentration. A well-defined porous activated carbon is obtained with a high surface area of 1081 m2g-1 and a high pore volume of 0.66 cm3 g-1 when the Quercus Suber/KOH was fixed at 1:2. A specific capacitance of 166 F g-1 was obtained for the symmetric device at 0.5 A g-1 in 1 M Na2SO4 with corresponding energy and power densities of 18.6 W h Kg-1 and 449.4 W Kg-1 respectively. The device displays good cycling stability after floating test for 200 h at 1.8 V and also displaying 99.8 % capacitance retention after 5000 charge/discharge cycles. The excellent electrochemical performance of the device makes it a potential material for supercapacitor application.

235

Carbon Fiber and Carbon Nanotube Multi-Scale Reinforced Epoxy Matrix Composites

Zhao, D L, Hu, T, Wu, L L, Cheng, X W



Carbon fiber (CF)-reinforced polymer composites have been extensively applied to the areas of aerospace, aircraft, rocket, sport and military industries due to the superior strength-to-weight, stiffness-to-weight ratio and high service temperature. It is quite beneficial to incorporate nanoscale fillers into polymer/CF systems to enhance mechanical properties of the composites. The carbon nanotubes (CNTs) were prepared by catalytic decompose of benzene using floating transition method at 1100-1200 . Benzene was used as carbon source and ferrocene as catalyst with thiophene. The carbon nanotubes are straight with diameter 20-50nm, internal diameter 10-30nm and length 50-1000 m. The carbon nanotube and continuous carbon fiber (T300) reinforced unidirectional epoxy resin matrix composites was fabricated. The volume fraction of continuous carbon fiber (first filler) in a composites without second filler (carbon nanotube) was 60%. The mechanical properties of the composites were investigated under bending, shear, and impact loading. The values of flexural strength were 1430 MPa with 0 wt% CNTs, 1450 MPa with 1 wt% CNTs, 1780 MPa with 3 wt% CNTs and 1120 MPa with 5 wt% CNTs at room temperature. The values of flexural modulus were 118 GPa with 0 wt% CNTs, 166 GPa with 1 wt% CNTs, 164 GPa with 3 wt% CNTs and 126 GPa with 5 wt% CNTs.

236

Carbon Foam with High Strength Derived from Pitch and Coal

Gao, S, Villacorta, BS, Ge, L, Rufford, TE and Zhu, Z


School of Chemical Engineering, The University of Queensland, Brisbane, Australia

Carbon foams with hierarchical pore structures, good thermal conductivity and electrical conductivity have been reported as promising materials for energy storage, catalyst supports, gas adsorption, and clean-up of oil spills. In many of these potential applications of carbon foams one of the technical challenges is to develop carbon foams with large pore volumes and good mechanical strength. In this study, we investigated the use of coal powders as modifier particles to prepare high-strength activated carbons foam discs from mesophase pitch. Potassium hydroxide was added as a chemical porogen to the mesophase pitch + coal mixture. The compressive strength of the carbon foam discs increased with the mass ratio of coal to pitch from 18.09 MPa at a coal:pitch ratio of 1:2 to 40.42 MPa at a coal:pitch ratio of 2:1. The BET specific surface area of the carbon foam prepared with coal:pitch ratio of 2:1 was 980 m2/g, but the total porosity of the carbon foams decreased from 66.9 % to 60.9 % when the coal ratio increase from 1:2 to 2:1. Our results support that mesophase pitch has a good potential as a precursor for carbon foams with high compressive strength. We found that the amount of coal particles had a strong effect on the mechanical properties of the carbon foam discs. The results suggest that the coal particles may contribute several roles as modifiers of the foaming processes including the stabilization of bubbles formed during foaming, and the supply of active catalytic sites during foam carbonization.

237

Carbon Membrane with High Gas Separation Performance for CO2 Capture Prepared from the Rigid olyimide

Li, L., Song, J., Lu, Y.H., Jin, X., Xu, R.S., Wang, C.L., Wang, T.H.

[email protected]

State Key Laboratory of Fine Chemicals, Carbon research Laboratory, School of Chemical

Engineering, Dalian University of Technology, Dalian 116024, China Carbon dioxide is the major greenhouse gases that makes global climate warming. The capture and controlling emission of CO2 have become a significant global issue. Membrane-based separation technology is more attractive in CO2 separation and capture due to its high efficiency, low energy consumption and environmental friendliness. However, the membrane materials with high CO2 permeability and selectivity is the most important in the commercial application of membrane technology for the CO2 capture. Carbon membrane is a kind of porous inorganic membrane materials with tuned pore structure, which can efficiently separate mixture gases based on the molecular sieving mechanism and hold promise in a number of gas separation applications. Carbon membranes are generally prepared by pyrolysis of polymeric precursors and the structure of precursor greatly affects the gas separation performance of the derived carbon membranes. A novel rigid polyimide precursor, the 6FDA (BAF: BAHF) (1:1), with phenol hydroxyl groups and high free volume was designed and synthesized to fabricate the carbon membrane. The changes of chemical and microstructures of precursor during carbonization and gas separation performance of derived carbon membrane were characterized. Results show that the carbon membrane prepared from polyimide of the 6FDA (BAF: BAHF) (1:1) at 550 showed a higher gas permeability，especially for CO2

permeation, which is up to 24770 Barrer with a CO2/CH4 selectivity of 29 and significantly higher than the Robeson upper bound. This indicates that the carbon membrane prepared from BAF:BAHF-6FDA based polyimide exhibits an attractive application prospect for the CO2 separation and capture.

238

Carbon Nanofiber Film as Binder-Free Anode Materials for Sodium-Ion Storage

Guo, X1, Zhou, J1, 2*, Song, H1, 2, Chen, X1

[email protected]



Jiangsu, P. R. China.

Sodium ion batteries (SIBs) are considered to be the most promising candidate for lithium ion batteries (LIBs), due to the similar properties between sodium and lithium and the abundance storage of sodium. However, searching for the stable and high capacity anode materials is still a challenge, because of the large scale ionic radius of sodium ion. In this study, novel PVP-based carbon nanofibers were synthesized by electrospinning process followed by thermal treatment. The structure and morphology of carbon nanofibers were mainly characterized by scanning electron microscopy (SEM), high-resolution transform electron microscopy (HRTEM), and X-ray photoelectron spectroscopy (XPS). As-prepared carbon nanofiber (CNF) film is flexible, and average diameter of CNFs is ca. 700 nm. More interestingly, CNFs in the film form a cross-linked (CL) structure, which should be related to the coordination between the PVP and Cu(NO3)2 during the electrospinning process. Remarkably, the CNFs with CL-structure demonstrated excellent rate performance and long cycle stability when used as binder-free anode for SIBs, compared with CNFs without CL-structure. At 50mAg-1, the CNFs with CL-structure delivered a specific capacity at 368mAhg-

1, which is higher than that of CNFs without CL-structure. And at 1 Ag-1, the reversible capacity still maintained 91mAhg-1 after 500 cycles. The perfect electrochemical properties of the CNFs films can be attributed to the unique cross-linked structure that enhanced electrochemistry stability and decreased contact resistance.

239

Carbon nanoparticle containing hydrogel nanocomposites with enhanced IR sensitivity

Barbara Berke1,2, Lionel Porcar2, Orsolya Czakkel2*, Krisztina László1

1Department of Physical Chemistry and Materials Science, Budapest University of

Technology and Economics, 1521, Budapest, Hungary 2Institute Laue Langevin, CS 20156, F – 38042 Grenoble Cedex 9, France

Hydrogels with environmental sensitivity can provide a way to change some of their properties (i.e. size, optical properties, etc.) in a controlled way making a perfect candidate for actuators, sensors or vehicles for drug delivery systems. Their physical properties often restrict the applicability of pure polymer systems, which can be overcome by nanocomposite hydrogels. Regardless of the targeted application, the comprehensive understanding and tunability of the nature and kinetics of the response is inevitable. Our aim was to investigate the effect of quality and quantity of carbon nanoparticles with different structure and surface chemistry on the thermal response of nanocomposite system. Carbon nanotubes (CNTs) and graphene oxide (GO), respectively, were incorporated into the poly(N-isopropyl acrylamide) gel matrix. Because of their unique structure, outstanding mechanical and conductive properties, they can act not only as reinforcing agents, but may provide new type of sensitivity to the systems. The observed effect of the two nanoparticles is significantly different. The presence of CNT does not alter the character of the response. GO at temperatures significantly higher than the temperature of volume phase transition (VPT) slows down the triggered shrinkage, while at temperatures just above the VPT its hydrophilic character facilitates the expulsion of water and results in a faster deswelling. The IR sensitivity was enhanced in composites. A monotonic correlation was found between the nanoparticle content and the temperature of the samples upon IR irradiation, but the concentration dependence was different for the two type of composite family.

240

Carbonaceous wires for neural interfacing

Apollo, NV1, Jiang, J1, Cheung, W1, Bacquier, S1, Mirebedini, A2, Foroughi, J2, Chen, S3, Williams, R1,3, Wallace, GG2, Prawer, S1, Cook, M1, Nayagam, DAX1,3, Garrett, DJ1


1 University of Melbourne, Melbourne, Australia 2 University of Wollongong, Wollongong, Australia

3 St. Vincent’s Hospital, Melbourne, Australia The long-term functionality of state-of-the-art neural interfacing devices is currently limited due to inflammation and trauma at the electrode-tissue interface. It is now well known that soft, flexible, and low-density materials evoke considerably less damage when interfaced with biological tissues, making carbon composites an interesting alternative to the inorganic, metallic standards. In this work, yarns based on graphene, carbon nanotubes, or both were assessed for their potential to function as neural interfacing devices. The yarns were assessed for adhesion and survival of hippocampal neuron cell cultures. Next, single probe depth electrodes were fabricated using a novel low-power laser excision method and were inserted into brain tissue using a water-soluble microneedle. Neural stimulation and recording were achieved in an in vitro setting. Both spontaneous and epileptic neural activity were recorded in acute and chronic in vivo experiments. Finally, biocompatible metallization techniques based on active brazing were developed to incorporate the yarns into biocompatible and biostable substrates based on polycrystalline diamond.

241

CO0.85Se Nanosheets/Graphene Composite Film as Binder-Free Anode for Lithium-Ion Batteries

Zhang, G1, Zhou, J1, 2*, Chen X1, Song, H1, 2

[email protected]



Jiangsu, P. R. China

Transitional metal selenides (TMSs) have attracted interest as anode materials for lithium-ion batteries (LIBs) due to their high capacities, thermal and chemical stability. Cobalt selenide, as one of most important TMSs, has been investigated as anode materials for LIBs. However, cobalt selenide anodes possess some drawbacks such as large volume expansion during the lithiation/delithiation process and poor cycle stability. Here, flexible free-standing Co0.85Se nanosheets/graphene (Co0.85Se-NS/G) composite film was prepared by a simple vacuum filtration and thermal reduction processes. In the Co0.85Se-NS/G composite film, Co0.85Se NSs were uniformly embedded within the graphene layers to form a “sheet-on-sheet” sand-wich structure. This hybrid lamellar composite film can be directly examined as a binder-free anode for LIBs and demonstrated high capacity and excellent rate performance. At a current density of 50 mA g-1, the initial reversible capacity of the Co0.85Se NSs/G composite film reached up to 680 mA h g-1 with the initial coulombic efficiency as high as 68.7%. At higher current densities of 1, 2, 5, and 10A g-1, the capacities are 478.3, 309.2, 222.3, and 102.5 mA h g-1 after 300 cycles, respectively. The excellent electrochemical performance should be attributed to the special “sheet-on-sheet” sand-wich structure, which provides not only an efficient electrically conductive pathways, but also acts as an elastic layer to buffer the volumetric expansion of Co0.85Se NSs during the lithiation/delithiation process.

242

CO2 Adsorption Study on Porous Materials by Adsorption Calorimetry

Moreno-Piraján, J.C1, Bastidas-Barranco2, M.J, Giraldo, L3

[email protected]

1 University of the Andes, Bogotá, Colombia 2 Universidad de la Guajira, Rioacha, Colombia

3Universidad Nacional de Colombia, Bogotá, Colombia In the current work, a set of different porous materials, including Metal Organic Frameworks (MOF's) and activated carbons obtained from Mangosteen Shell was studied. The MOF's featured high stability and reproducible performance in the CO2 adsorption/desorption tests. Furthermore, the maximum CO2 adsorption capacities of the activated carbons prepared from mangosteen shell in this research were found to be comparable or superior to some samples of MOF's synthesized. Additionally, the results also showed that the adsorption and desorption are very fast, a feature suitable for future applications of these MOF's in CO2 capture. To further illustrate the critical role of porosity of each material prepared in this work in the CO2 uptake, the isosteric heat of adsorption (Qst) is calculated by applying Clausius–Clapeyron equation to the CO2 adsorption isotherms at several temperatures. The Qst value reflects the interaction strength between CO2 and carbon adsorbents. In addition, differential adsorption heats between CO2 and porous materials have been experimentally determined by the use of an adsorption calorimeter (ad-cal) ("home-made"). The calorimetric results were compared with the isothermal heats and to analyse the differences between these two methods.

243

CO2 Electroreduction Using Boron-Doped Diamond (BDD) In Different Electrolyte

Maulana Ichsan, A1, Tri Lestarini, D1, Ratna Endriana, A1

[email protected]

1Universitas Indonesia, Depok, Indonesia

Climate change due to the gradual increase of CO2 concentration level in the atmosphere had become a worldwide concern. Various methods had been applied in order to reduce CO2 concentration in the atmosphere, one example is the electrochemistry method. This method is classified as green method as only electrical energy and electrolyte are necessary in the process. On the other hand, boron-doped diamond (BDD) is known as an electrode with many advantages, such as physical and chemical stability, wide potential window, extremely low background current, biocompatible, and relatively insensitive toward dissolved oxygen. The objectives of this study are to observe the ideal electrolyte for electrochemical reduction of CO2 and to investigate the performance of BDD electrode in reducing CO2. The study was conducted at BDD electrode in various electrolytes, including NaCl, KCl, Na2CO3, and K2CO3. Cyclic voltammetry showed that the promising electroreduction activity is obtained by NaCl with a peak reduction potential of 1.7 V (vs Ag/AgCl). The electroreduction results, which were examined by chromatography techniques and showed that NaCl is potential as electrolyte for CO2 electroreduction using BDD electrode.

244

CO2 Electroreduction Using Boron-Doped Diamond (BDD) In Different Electrolyte

Maulana Ichsan, A1, Tri Lestarini, D1, Ratna Endriana, A1

[email protected]

1Universitas Indonesia, Depok, Indonesia

Climate change had become a worldwide concern. One of the main causes is the gradually increasing of CO2 concentration level in the earth’s atmosphere each year. Data showed that CO2 concentration reached 403.64 ppm as of November 2016. Therefore, CO2 electroreduction was studied with different electrolytes such as NaCl, KCl, Na2CO3, and K2CO3 through electrochemistry process. The objective of this study is to understand the ideal electrolyte for CO2 electroreduction and to investigate the performance of Boron-Doped Diamond (BDD) in reducing CO2 with electrochemistry method. This method was chosen in this study primarily because CO2 reduction reaction is initially unspontaneous thus electric energy would be needed to reduce it forming other green chamicas. Electrolyte solutions, previously bubbled with N2 for 15 minutes and CO2 with various time of 15 minutes and 30 minutes, concentrated at 0.1 M. BDD was used as the working electrode. BDD is known for having several advantages over any other electrodes such as higher stability, broad working potential, low background current, biocompatible, and relatively insensitive to dissolve oxygen. The most ideal electroreduction activity was achieved by NaCl electrolyte with CO2 bubbling duration of 30 minutes. A peak reduction appeared at -1.764 V (vs Ag/AgCl) observed by cyclic voltammetry technique. Therefore, NaCl is a feasible electrolyte for CO2 electroreduction. This system could be developed to become a green process with the usage of seawater as it contains NaCl electrolyte.

245

Coal-Tar-Pitch Mesophase Formation Effect Study According to the Heat-Treatment Heating-Rate

Sang-Min Lee, Dong-Su Kang, Un-Gyeong Baek, Jae-Seung Roh*

[email protected]

School of Materials Science and Engineering, Kumoh National Institute of Technology, Gumi, South Korea

Coal tar pitch is synthesized by the polymerization of coal tar, which is produced during coal carbonization. Coal tar pitch has high carbonization yield, low cost, and excellent properties, and a diverse range of industrial applications, including carbon fibers and artificial graphite binders. During the fabrication of carbon and graphite products using coal tar pitch, swelling ccurs due to a phase change induced by the carbonization reaction. Studies have reported using various modifications and carbonization reaction times in attempts to control such swelling. In this study, changes in microstructure and crystallinity were analyzed based on the heating rate in the temperature range of around 400 ~ 450 where the mesophase with optical anisotropy is formed. It was predicted that the heating rate would affect the mesophase nucleation, growth, and agglomeration stages. In this study, observations were made at varying heating rates of 1 /min, 5 /min, and 9 /min up to 400 . The microstructure was observed under polarized light using an optical microscope and the crystallinity was investigated by XRD and Raman analyses. The crystallinity analysis investigated the plane spacing and crystallite size.

246

Compaction and Better Alignment of Carbon Nanotube Fibres

Cho, H1, Lee, J1, Lee, S-H1, Lee, K-H1,

[email protected]

1 POSTECH, Pohang, Republic of Korea While the length of carbon nanotube (CNT) is too short, CNT fibres have no limitation on length. However, their properties do not reach the own properties of CNT. Two main reasons are micro-size voids and poor alignments of CNT bundle. To solve this problem, CNT fibres have been compacted and stretched with the existence of solvents to enhance mechanical properties. Bundle to bundle distances were decreased using a physical rolling method which reduces pore volume and maximizes van der Waals force. The Solvent was injected to nip rollers while compacting the CNT fibre to give additional compacting effect known as the action of liquid bridging (capillary forces). After that, stretching process was done. Comparatively weak sonication (1.5 W/cm2, 40 kHz) for the short time (0~12 sec) was conducted to increase infiltration of solvent into the fibre. The solvent bearing fibre is wound up with the set velocity to stretch the fibre. Cross-sections of CNT fibres were observed using focused ion beam (FIB) and SEM which confirmed that the micro-pores were efficiently removed. The median and average values of bundle to bundle distances were both decreased to one third after the compaction. Polarized Raman spectroscopy confirmed the alignment of CNT fibres. Their alignments enhanced as the sonication time and winding rate increase up to the optimum points. Specific strength (N/tex) measured using Favimat (gauge length: 20mm) was 1.08 N/tex, which is about 3 times of the pristine CNT fibre.

247

Comparison of Carbon Nanomaterials for Catalyst Support Property

Suda, Y1, Harigai, T1, Takikawa, H1, Umeda, Y2


1 Toyohashi University of Technology, Toyohashi, Japan 2 Chubu Region Institute for Social and Economic Research, Nagoya, Japan

PtRu or Pt catalysts were supported on four types of carbon nanomaterials with different shapes, sizes, and graphitic and electrical properties, and their resulting catalytic activities were evaluated by electrochemical methods. The carbon nanomaterials used included two types of particles: Arc Black (AcB) and Vulcan XC-72R (Vulcan), and two types of nanofibers: carbon nanocoils (CNC) and VGCF-X. Pt and Ru were loaded onto the nanomaterials by a reduction method using sodium borohydride. Transmission electron microscopy and X-ray diffraction (XRD) revealed the PtRu catalyst particles to be 4–6 nm in diameters. The shifts in the Pt (111) XRD peaks of the catalysts on CNC and VGCF-X were larger than those on AcB and Vulcan, indicating a higher degree of alloying between Pt and Ru. The diameters of the CNC-supported Pt and PtRu catalyst particles had the narrowest distributions and were constant within the range of catalyst loadings investigated. Electrochemical studies of the catalysts during methanol oxidation were carried out using cyclic voltammetry. The catalyst particles supported on CNC and VGCF-X exhibited higher catalytic activity than those on AcB and Vulcan. The effect of the surface area of the carbon nanomaterials on the catalytic activity is discussed.

248

Construction of integrated RGO/MnFe2O4/g-C3N4 catalyst for efficient decomposition

of methylene blue

Jiangying Qu,1,* Feng Gao, 1 Xiyue Peng,1 Yuqian Li,1 Guifa Jiang 1, Mingbo Wu2,* and

Jieshan Qiu3


1 Faculty of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian, Liaoning, 116029, China

2 State Key Laboratory of Heavy Oil Processing, School of Chemical Engineering, China University of Petroleum, Qingdao, 266580, China

3 Carbon Research Laboratory, Center for Nano Materials and Science, School of Chemical Engineering, State Key Lab of Fine Chemicals, Dalian University of Technology,

Dalian 116012, China MnFe2O4 mediated reduced graphene oxide (RGO) and g-C3N4 sandwich-like hybrid (RGO/MnFe2O4/g-C3N4) has been successfully constructed as an effective Fenton-like catalyst. The designed RGO/MnFe2O4/g-C3N4 hybrid integrates the high catalytic activity and magnetic recovery of MnFe2O4, the good adsorption capacity of RGO as well as the sensitive visible light absorption capability of g-C3N4. It is found that the formation of C–O–C bonds and π-π interaction between RGO and g-C3N4 as well as the Fe–N and Mn–N bonds between MnFe2O4 and g-C3N4 leads to the strong interactions between RGO, MnFe2O4 and g-C3N4 in RGO/MnFe2O4/g-C3N4 hybrid. The integrated RGO/MnFe2O4/g-C3N4 hybrid shows excellent catalytic performance towards the decomposition of methylene blue (MB). Typically, 50 mL MB (50 mg L-1) can be 100% decolorized within 80 min in the presence of H2O2 at room temperature and the catalyst remains 99% decolorizition in the fourth run. This strategy to constructe RGO/MnFe2O4/g-C3N4 hybrid provides a logical framework for the hybrid design and its functionalization.

249

Continuous and Flexible Graphene-Based Fibrous Cathode for Lithium Sulfur Batteries

Chong, WG1, Huang, JQ1, Xu, ZL1, Qin, X1, Wang, X1, Kim, JK1


Department of Mechanical and Aerospace Engineering 1 The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong

Kong

The development of wearable technology is one of the major growth areas for flexible batteries which require high energy densities and shape amenabilities. Previous studies of flexible batteries may meet the energy requirements but with a trade-off between the low areal capacity, poor mechanical stability and large thickness of inactive components. A wet-spinning assembly strategy is developed to produce continuous graphene-based composite fibrous cathode consisting of reduced graphene oxide/carbon nanotubes filled with a large amount of sulfur (rGO/CNT/S) for rechargeable lithium sulfur batteries [1]. The incorporation of GO liquid crystal renders a unidirectional alignment of rGO/CNT/S composite, enabling the rational assembly of flexible and conductive fibres as electrodes. The highly conductive fibres are mechanically robust with a tensile strength of 20 MPa and the electrical conduction is unaffected even after 100 bending cycles. The one dimensional fibrous electrodes with scalable linear densities ranging 0.028-0.13 mg cm-1 deliver a high initial capacity of 1255 mAh g-1 and an areal capacity of 2.49 mAh cm-2 at C/20. The high stability of the electrochemical performance under cyclic bending and excellent mechanical flexibility of the fibrous LSBs highlight great potential of graphene-based fiber assemblies in search for shape-compliant electrode materials. [1] W.G. Chong, J.Q. Huang, Z.L. Xu, X Qin, X. Wang, J.K. Kim. “Lithium sulfur battery cable made from ultralight, flexible graphene/carbon nanotubes/sulfur composite fibers” Adv. Funct. Mater. (2017) 1604815 DOI: 10.1002/adfm.201604815

250

Control of pore structures in MgO-templated carbons for EDLCs

Kado, Y., Soneda, Y.


Research Institute of Energy Frontier, National Institute of Advanced Industrial Science and Technology, Tsukuba, JAPAN

MgO-templated carbons were synthesized via calcination of trimagnesium dicitrate nonahydrate by heating to 1000°C at different heating rates, followed by acid leaching of MgO. Pore structures of the obtained carbons were evaluated by N2 adsorption isotherm. A faster heating produced a greater amount of mesopores in the carbons. A slower temperature increase provided a higher carbonization yield, suggesting that generated MgO particles were effectively covered with carbon. It is therefore considered that growth of MgO particles as templates was suppressed and small mesopores were formed in the final products. Thus, the pore structures of MgO-templated carbons are controllable by changing the heating rate during calcination of magnesium citrate. Performance as electrode materials for electric double-layer capacitors were investigated in organic electrolytes. The carbons obtained at a ramping rate of 1°C min−1 exhibited a relatively large volumetric capacitance comparable to that of commercial activated carbons. In addition, they exhibited a better rate capability due to the presence of mesopores.

251

COR and OER of Several Carbon Materials in KOH Solution

Taro Kinumoto*, Makoto Eto, Kohei Ono, Miki Matsuoka, Tomoki Tsumura, Masahiro Toyoda


OITA UNIVERSITY, OITA, JAPAN

Both of carbon oxidation reaction (COR) and oxygen evolution reaction (OER) for Ketjen black (KB), natural graphite (NG), vapor grown carbon fiber (VGCF) are investigated in KOH aqueous solution by using a rotating disk ring electrode. The onset potentials for COR and OER are determined and the reaction kinetics, especially the weight loss rate ascribed to COR, are also evaluated. For instance, the onset potentials of VGCF are clarified as 0.40 V against Hg|HgO for COR and as 0.68 V for OER, respectively. In the case of NG, the onset potentials are close to the values of VGCF as 0.40 V for COR and 0.66 V for OER. On the other hand, in the case of KB, the onset potentials are lower than the results of NG and VGCF and are determined as 0.23 V and 0.63 V for COR and OER, respectively. The weight loss rate of VGCF is estimated as 0.002 % h-1 - 0.007 % h-1 at 0.6 V, which is the quite lower than that of Ketjen black. In addition, we also investigated COR and ORR in the steady-state condition by using a DO sensor. The results give guidance for carbonaceous materials to use in the positive electrode of the rechargeable air battery where an alkaline medium is employed. The effects of LaMnO3 (known as the catalyst for OER) will be also presented.

252

Reation of Micro and Nano Spaces by Mixture of Dissimilar Materials and Electro Spinning

Oshida, K1, Fujisawa, T1, Minamizawa, T1, Kobayashi, N1, Shimokoshi, T1, Itaya, T1,

Osawa, K1, Murata, M1, Hata, T2, Takeuchi, K3, Fujishige, M3, Endo M3


1 National Institute of Technology, Nagano College, Nagano, Japan 2 Research Institute for Sustainable Humanosphere of Kyoto University, Uji, Japan 3 Institute of Carbon Science and Technology, Shinshu University, Nagano, Japan

In order to develop high functional electrode materials and functional adsorbents for molecular sieving, dissimilar materials were mixed and micro-, naono-spaces were created. the structures of them were analysed by transmission electron microscopy (TEM) and image processing. Poly acrylic nitrile (PAN) and Hydroxypropyl Cellulose (HPC) were dispersed in dimethyl formamide (DMF) and nano fibers were prepared by electrospinning. The diameters of fibers are from 200 to 300nm, These fibers were stabilized at 240°C and carbonized by heat-treatment at 1000°C (5°C/min). So as to remove the HPC and to make micro- and nano-spaces, the sample were washed in the water before stabilizing it. The melted part of the HPC turns to the spaces. Other several dissimilar materials were mixed to make nano and micro spaces. Structure of the carbon nano fibers was analysed by TEM. Convoluted hexagonal carbon layers of the nano fibers were observed on the surface of them. As the result of electrospinning, large number of nano spaces was created. There were also observed large sized metho pores. 2 dimensional fast Fourier transform (2D-FFT) was applied to the TEM images. Power spectra obtained from the 2D-FFT were converted to graphs by integration in the rotation direction around the center points of them. Specific surface areas (SSAs) and pore size distributions of the samples were measured. Thus the structure of the nanofibers were analysed quantitatively.

253

Cross-linking of the carbon nanotube fiber using azelaic acid dichloride

Lee, J1, Lee C-H1, Cho, H1, Lee, S-H1, Lee, K-H1*

[email protected]

1 Pohang University of Science and Technology, Pohang-si Gyeongsangbuk-do, South Korea

The carbon nanotube (CNT) has outstanding strength and electrical and thermal conductivities. However, the short length of the CNT limits the field of use. The CNT fiber is one way to overcome the length limitation of the CNT. The CNTs are simply in contact or twisted with each other inside of the CNT fiber, but chemical bonding is not formed between adjacent CNTs. Due to this, the strength of the CNT fiber is much lower than that of CNTs, so post-treatments included cross-linking are surely required. Cross-linking and compaction are the effective methods to enhance the strength of the CNT fiber. CNTs, which compose the CNT fiber, are assembled with van der Waals forces. Cross-linking makes additional covalent bonds between the CNTs, so the interaction between the CNTs is enhanced. Compaction of the CNT fiber also enhances the strength of the CNT fiber by removing the void in the CNT fiber. Elastocapillary effect induces the CNT fiber to be compacted. In this work, the strength of the CNT fiber is enhanced using azelaic acid dichloride. Azelaic acid dichloride used as a linker for cross-linking reaction between the CNTs as well as liquid to compact the CNT fiber by elastocapillary effect. Azelaic acid dichloride oxidizes the surface of the CNT and the surface reacts with acid chlorides in azelaic acid dichloride to connect the CNTs. In addition, azelaic acid dichloride is liquid, so it infiltrates into the CNT fiber and compacts the CNT fiber using elastocapillary effect.

254

Crumpled Graphene-Encapsulated Coni-Layered Double Hydroxides Microspheres for High-Performance Lithium Storage

Shi, L, He, R, Chen, G, Chen, Y, Chen, X and Song, H*


* Corresponding author’s e-mail: [email protected]

State Key Laboratory of Chemical Resource Engineering, Beijing Key Laboratory of Electrochemical Process and Technology for Materials, Beijing University of Chemical

Technology, Beijing 100029, PR China

Crumpled graphene-encapsulated CoNi-layered double hydroxides microspheres (CG-LDH) as an anode material for high-performance lithium ion battery (LIB) is synthesized by a facile strategy. CoNi-LDHs self-assemble into the microspheres in deionized water solution and are encapsulated by the crumpled graphene as the shell. The process is driven by the mutual electrostatic interactions of these two components. When investigated as the LIB electrode, the CG-LDH shows a high capacity of ~1000 mA h g-1 at the current density of 50 mA g-1, and even 240 mA h g-1 at the current density of 10 A g-1. The cycle stability is good with the capacity retention of ca. 100% after 110 cycle. The excellent performance of CG-LDH electrode would be ascribed to the graphene shell in accommodating the volume changes of metal ions, keeping the stucture more stable and improving the conductivity.

255

Crystalline Structure Variation of Phenolic-Resin According to Heat Treatment Conditions

Dong Su Kang, Sang Min Lee, Jae Seung Roh

[email protected].

Kumoh National Institute of Technology, Gumi, Gyeongbuk, Korea.

Phenolic resin is widely used as a binder of bulk graphite material and a precursor of glassy carbon. When heated above 500 , phenolic resin releases volatile substances and is carbonized. The crystallographic structure of carbonized phenolic resin was reported to exhibit short range graphitic structures and the graphitic structure does not show growth even when heated to above 2000 . Generally, carbon materials that do not form outstanding graphitic structures when heated to temperatures above 2000 are categorized as hard carbon. In this study, the heat treatment conditions such as heat treatment temperature and heating rate were varied to observe the macroscopic heat treatment behavior of phenolic resin. Furthermore, changes in the crystallographic structure of carbonized phenolic resin were observed using an XRD analysis and the variations of La, Lc, and plane spacing were analyzed.

256

Cu-doped carbon nanofibers as non-enzymatic glucose biosensor electrode

Sangmin Lee, Ji-Hyun Kim, and Young-Seak Lee*

Department of Chemical Engineering and Applied Chemistry, Chungnam National University, Daejeon, 34134, Korea

(*[email protected])

Glucose biosensor design is an active area of research whose aims is to enhance sensor performance. Enzymatic glucose sensors have been widely studied due to their high sensitivity and selectivity. However, thermal stability, chemical stability, and reproducibility are poor due to intrinsic nature of enzymes. In this study, to overcome these drawback, we fabricate non-enzymatic glucose sensor using Cu-doped carbon nanofibers (CNFs), which were prepared by electrospinning from polyacrylonitrile (PAN), dimethylformamide (DMF) and copper sulfate (CuSO4). The prepared sample were analyzed by X-ray diffraction (XRD) to confirm their crystal structure and energy dispersive X-ray spectroscopy (EDX) to investigate their elemental composition. The biosensor electrodes fabricated using the Cu-doped CNFs were shown to have high sensitivity in the range of 74.6 - 225.4 4 μAmM-1cm-2 and a low limit of detection (LOD) range from 0.4 - 2.66 mM.

257

CVD Assembly of 3d Graphene for Lithium-Sulfur Batteries

Qiang Zhang1,*



Among various promising candidates with high energy densities, lithium-sulfur (Li-S) batteries with a high theoretical capacity and energy density are highly attractive;1-2 while the commercial application of Li-S batteries still faces some persistent obstacles, such as the low electrical conductivity of sulfur and lithium sulfide and the dissolution of polysulfides. The introduction of 3D graphene into the field of Li-S batteries sheds a light on the efficient utilization of sulfur by improving the conductivity of the composites and restraining the shuttle of polysulfides. In this presentation, the concept for the rational design of 3D graphene is explained. The advances in the use of 3D graphene in the cathode, separator, and anode is explained.3-12 New insights on the relationship between the 3D graphene structure and the electrochemical performance are presented.

References

1) Manthiram A, Chung SH, Zu CX. Adv Mater 2015, 27, 1980.

2) Liang J, Sun ZH, Li F, et al. Energy Storage Mater 2016, 2, 76

3) Zhao MQ, Zhang Q, Huang JQ, et al. Nature Commun 2014, 5, 3410.

4) Cheng XB, Huang JQ, Zhang Q, et al. Nano Energy 2014, 4, 65.

5) Tang C, Zhang Q, Zhao MQ, et al. Adv Mater 2014. 26, 6100.

6) Zhao MQ, Peng HJ, Tian GL, et al. Adv Mater 2014, 26, 7051

7) Yuan Z, Peng HJ, Huang JQ, et al. Adv Funct Mater 2014, 24, 6105.

8) Zhao MQ, Liu XF, Zhang Q, et al. ACS Nano 2012, 6, 10759.

9) Cheng XB, Peng HJ, Huang JQ, et al. ACS Nano 2015, 9, 6373.

10) Huang JQ, Zhuang TZ, Zhang Q, et al. ACS Nano 2015, 9, 1506.

11) Peng HJ, Zhang Q. Angew Chem Int Ed 2015, 54, 11018.

12) Zhai PY, Peng HJ, Cheng XB, et al. Energy Storage Mater 2017, 7, 56

258

Deconvoluting Pseudocapacitance From Double Layer Capacitance in Nitrogen Doped Supercapcitors

Kenneth G. Latham1, Scott W. Donne1

Presenting author’s e-mail: [email protected] .

1 University of Newcastle, Newcastle, Australia

Activated carbons are the main choice of electrode material for electrochemical capacitors in commercial devices, due to their large surface area, reasonable electrical conductivity and relatively low cost. However, the capacitance of commercial activated carbon electrochemical capacitors is still relatively low (~180 F g-1) compared to other electrochemical capacitors (RuOx up to ~1500 F g-1). Increasing the surface area of activated carbons is met with demising returns in capacitance above 1500 m2 g-1. Thus, focus for carbon electrochemical capacitors has shifted towards either producing carbons with tuned levels of meso- and microporosity or integrating heteroatoms (i.e., nitrogen) into the carbon structure to introduce pseudocapacitance. Currently, there are significant limitations in determining the actual effect of pseudocapacitance on hydrothermal carbons. Quantitatively identifying electrochemical contributions from redox active sites using standard electrochemical methods, such as cyclic voltammetry, is almost impossible. This is due to the inability to separate the capacitance contribution from the double-layer, pseudocapacitance and electrolyte reactions. Recently, the application of Step Potential Electrochemical Spectroscopy (SPECS) to activated carbon, manganese dioxide and nitrogen doped activated carbon, has been shown to be able to effectively separate the various charge storage processes occurring on these materials. The SPECS analysis on the activated carbon revealed that the main capacitance contributions were from the double layer charge storage, however, pseudocapacitance was observed due to oxygen functionalities on the surface. For the nitrogen doped carbon, pseudocapacitance increased with reducing oxygen concentration, suggesting that the presence of oxygen may be detrimental to charge storage on these materials.

259

Deposition of Copper Nanoparticles On Ozone Pre-Treated MWCNTs In Fluidized-Bed CVD

Lassègue, P.1, Noé, L.2, Monthioux, M.2, Caussat, B.1


1Laboratoire de Génie Chimique, Université de Toulouse, CNRS, INPT, UPS, Toulouse, France

2CEMES, UPR CNRS 8011, Université Toulouse III, Toulouse, France In the field of aeronautics, the mass reduction of the on-board electronic equipment packaging is of major importance to make planes greener. To produce lighter packaging while keeping their electrical and thermal evacuation capacities and mechanical properties, a new composite material combining carbon nanotubes (CNTs) and polymer matrix represents a promising alternative to aluminium. The aim of this work is to improve the electrical and thermal conductivities of Multi-Walled CNTs, and consequently those of the final composite material, by depositing homogeneously dispersed nanoparticles (NPs) of copper on the MWCNT surface. Prior to copper deposition, Graphistrength®C100 MWCNTs tangled in porous balls of ca. 400 micrometres were oxidised in fluidized bed using a gaseous mixture of ozone, water vapor, and oxygen in order to increase their surface reactivity by grafting oxygen-containing groups and creating moderate structural defects uniformly on the MWCNT surface. 100 g of MWCNTs were treated for each experiment in a fluidization reactor at ambient temperature and atmospheric pressure. The same reactor was used to deposit copper NPs from Cu(acac)2 between 250°C and 280°C at atmospheric pressure, on both raw and pre-treated MWCNTs. On the raw MWCNTs, polycrystalline Cu NPs of several hundreds of nanometres are only present at the MWCNT ball surface over ~40 micrometre depth. With pre-treatment, the deposition of (much smaller, 20-50 nm) polycrystalline Cu nanoparticles occurs more uniformly both over the MWCNT surface and deeper inside the balls. The work demonstrates the upscalability of the process as a reasonably green and low cost technology.

260

Detection of cracks in graphene by scattering parameter measurements

Kang, T. Y1,2, Seo, D1, Yoon, T2, Kang, S2, Kim, T.–S2

[email protected]

1 Agency for Defense Development, Taean, Korea 2 Korea Advanced Institute of Science and Technology, Daejeon, Korea

The extraordinarily high carrier mobility in graphene makes it an attractive material for radio frequency (RF) electronics. However, the performance is limited by the defects in graphene such as grain boundaries, pinholes and cracks. The scattering parameter measurements using network analyzers are the most basic work of RF engineering. Thus, it would be highly convenient if the defects could be detected and analyzed by the s-parameter measurement itself. Here, we present the feasibility of the RF analysis as a method for detecting defects in graphene. In this study, the s-parameter measurements on both pristine and defected graphene specimens were compared and analyzed. The specimens were precisely defected with 3 - 7 macroscale cracks and microscale ones introduced by 2.5% - 7.5% strain. First, the measurement on bare graphene materials show the inductance characteristic which is represented by decrease in S21 parameters with increasing frequencies. Then, the RF analysis on the cracked specimens reveals that S21 values in the low frequency region drop as much as increase in the DC resistivity. Moreover, the S21 parameter of the cracked specimens decreases more with increasing frequencies than that of the bare specimens, which means that the defects affect not only resistivity but also inductance of graphene materials. This trend becomes more prominent with microscale cracks than macroscale ones. Inductance depends mostly on the shape of cracks. Therefore, the experimental results suggest that scattering parameter studies can be performed to catch a glimpse of both the amount and geometry of defects in graphene materials.

261

Development and Obtaining of Granulated Carbon Sorbents

A.R. Kerimkulova1,2, S.Azat1,2 , J.M.Jandosov1,2, M.R.Kerimkulova1, Z.A.Mansurov1,2

(1 Institute of Combustion Problems, 172 Bogenbay batyr Str, 050012 Almaty,

Kazakhstan 2Al-Farabi Kazakh National University, 71 Al-Farabi Ave., 050040 Almaty,

Kazakhstan)

[email protected]

Production of carbon sorbents is exceptional importance for elimination of consequences of man-made and anthropogenic activity of people. Carbon sorbents are widely used in various fields of national economy, in particular for separating gas mixtures and the recovery of vapors of volatile solvents. The main raw materials are traditional natural carbonaceous materials for the production of carbon sorbents: fossil coal, peat, wood, and waste their processing - lignin, agricultural waste and others. The properties of carbon sorbents are directly dependent on the used raw materials and developed in the its processing in the active carbons, main stages which are carbonation - thermal degradation of the starting material to create a porous primary structure and strength properties of the product, and activation - high temperature oxidation agent combined cycle (steam and gas or physical activation) or treatment with chemicals (chemical activation) in order to develop a predetermined pore structure throughout the volume of activated particles. Currently, very important the development of carbon sorbents with high mechanical strength and high sorption characteristics, including the new non-traditional raw materials, natural and synthetic carbon materials.

Therefore in the present work we have investigated the possibility of producing sorbents based on agricultural waste and industrial waste by extrusion, granulation in a liquid medium. As the use of agricultural waste from rice husk flour and lignin sulfonate, which is a waste of pulp and paper industry. Selected optimal granulation regimes with a binder - lignosulfonate. Pick up a weight ratio of rice husk flour and binder. Investigated physico-chemical properties of the pellets before and after heat treatment: elemental composition, surface area and microstructure.

262

Doped Carbon Materials as Electrocatalysts For the Oxygen Reduction Reaction

M.J. Nieto-Monge1, J.C. Ruiz-Cornejo1, D. Sebastián1, C. Alegre1,2, M.V. Martínez-Huerta3, E. Pastor4 and M.J. Lázaro1

[email protected]

1Instituto de Carboquímica (CSIC), Miguel Luesma Castán 4, 50018 Zaragoza, Spain 2Istituto di Tecnologie Avanzate per l’Energia “Nicola Giordano” (CNR), Via Salita S. Lucia

sopra Contesse 5, 98126 Messina, Italy 3Instituto de Catálisis y Petroleoquímica (CSIC), Marie Curie 2, 28049 Madrid, Spain.

4Instituto de Materiales y Nanotecnología. Universidad de La Laguna. Avda. Astrofísico Francisco Sánchez s/n. 38206 La Laguna, Tenerife, Spain

Nowadays, carbon materials are used as catalyst support in different energy conversion devices, such as polymer electrolyte membrane fuel cells (PEMFCs). Carbon blacks are the most commonly used in the field of electrocatalysis due to their good characteristics. Nonetheless, other novel carbon nanostructures are being investigated because they offer enhanced structural and textural properties for this purpose. Moreover, doping carbon materials with heteroatoms like nitrogen or sulphur appears as a promising strategy to further improve their behaviour as catalyst support. Additionally, recent works have also pointed out a significant electroactivity for the oxygen reduction reaction of nitrogen-doped carbon materials without the noble metal active phase, which supposes a breakthrough towards cost-efficient fuel cell systems. In this work, carbon blacks, carbon nanofibers and/or carbon xerogels are chemically treated to introduce nitrogen or sulphur functionalities within the carbon surface/matrix. An oxidation process in strong acid appears as a required step to increase hydrophilicity of carbon. Afterwards, some nitrogen containing substances have been studied as precursors, like ethylenediamine, cyanamide, melamine, urea, pyrrole or ammonia. The right choice of treatment conditions and precursor nature relies on the carbon material characteristics. In the case of sulphur, elemental sulphur or sulphurised compounds are investigated as precursors. The catalytic activity of these doped carbon materials, both with and without active phase (Pt-based), towards the oxygen reduction reaction is electrochemically evaluated in acid and alkaline environment and discussed with regard to the incorporation of N and S heteroatoms.

263

Durability of carbon based electrocatalysts for PEMFC application. Influence of the graphitization level and fluorination treatment

Guérin, M1,2, Batisse, N1,2, Dubois, M1,2, Molina Concha, B4,5, Maillard, F4,5, Chatenet M4,5,

Labbé F3 , Metkemeijer R 3, Berthon-Fabry S3


1Clermont Université, Université Blaise Pascal, Institut de Chimie de Clermont-Ferrand, BP 10448, F-63000 Clermont-Ferrand, France

2CNRS, UMR 6296, Institut de Chimie de Clermont-Ferrand, F-63171Aubière, France 3 MINES ParisTech, PSL Research University PERSEE - Centre procédés, énergies

renouvelables et systèmes énergétiques, CS 10207 rue Claude Daunesse F-06904 Sophia Antipolis Cedex, France

4 Univ. Grenoble Alpes, LEPMI, F-38000 Grenoble, France 5 CNRS, LEPMI, F-38000 Grenoble, France

. Proton exchange membrane fuel cells (PEMFC) are energy converters that can be used in nomad, automotive or stationary applications without emission of pollutants. The insufficient durability is strongly linked to the corrosion of the carbon support in the cathode electrocatalyst. It is particularly observed under high potential and especially during start/stop phases of the cell. It leads to the detachment and agglomeration of the catalyst nanoparticles, the decrease of the carbon hydrophobicity that adversely affects the water management and the collapse of the carbon structure, phenomena that increase mass-transport losses. In this study, firstly, we related the impact of the textures and the structure of different carbons on the durability of the resultant electrocatalysts. Graphitic carbons are more resistant to oxidation, whereas greater specific surface areas are more favorable to the dispersion of a large amount of catalyst nanoparticles per unit volume. Secondly, these model materials were modified by surface treatment in order to increase their durability by increasing their hydrophobicity through controlled fluorination. The objective was to limit the corrosion induced by the surface oxygen content and the electrolyte, by saturating dangling bonds with fluorine.The samples were texturally, morphologically and chemically characterized by XRD, TEM, nitrogen sorption, FTIR and TGA. The catalytic activity of these electrocatalysts towards the oxygen reduction reaction was determined by linear sweep voltammetry and start-up/shutdown protocols. The results and the impact of the fluorination are discussed and compared to those for a 40 wt% commercial state-of the-art electrocatalyst.

264

Durability of graphene-coated-carbon-fiber-cloth-supported platinum as PEFC electrode

Arai, Y1, Kudou, D1, Nagata, T2, Sutani, K2, Kinumoto, T1, Tsumura, T1, Muramatsu, K2,

Toyoda, M1


1 Department of Applied Chemistry, Faculty of Engineering, Oita University, Oita, Japan. 2 Incubation Alliance Inc., Kobe, Japan.

Polymer electrolyte fuel cells (PEFCs) have been recently attracting much interest because they are efficient and non-polluting power sources for vehicles. However, reducing the amounts of platinum in their electrodes and enhancing the electrode’s durability are important problems that need to be solved to enable the practical use of PEFCs. Carbon-supported platinum is commonly used as catalyst for PEFCs; however, carbon-supported platinum suffers low platinum-utilization efficiency because of the platinum residing in the pores of the carbon. Furthermore, the carbon exhibits poor durability because of low degree of graphitization. Graphene has been considered as a potential candidate to mitigate these problems as it exhibits high electron conductivity and high graphitization degree and is non-porous. In this study, graphene-coated carbon fiber cloth (GCFC) was used as a carbon-support. GCFC which was synthesized via hot isostatic pressing method, contains vertically oriented graphene fibers that uniformly stood on the surface of carbon fibers. Electrodes were obtained by platinum sputtering on GCFC and carbon paper. The durability test was performed using a three electrode cell in 1 mol dm-3 H2SO4 as the electrolyte. The retention rate of the electrochemical surface area (ECSA) was greater than 90% even after the durability test of the platinum-sputtered GCFC used as an electrode. In contrast, the retention rate was less than 60% for the platinum-sputtered carbon paper used as an electrode. Durability tests were also performed using a PEFC standard cell. The durability of the platinum-sputtered GCFC was found to be 6 times higher than that of the commercial catalyst.

265

Easy and simple method to produce large single layer graphene

Kim H-R1, Lee S-H1 and Lee K-H1

[email protected]

1 POSTECH, Pohang, Korea

Graphene became the hottest issue over the last 10 years because superior electrical, optical and thermal properties are included in just one material. There have been many accomplishments in graphene research, however, the actual commercialization is hard to find yet. For the commercialization, superior property and price competitiveness must be satisfied simultaneously. Since the current graphene production technology does not satisfy this requirement, continuous research on production technology is essential. Top-down method starting from graphite is attracting attention as a technology for commercialization due to its high productivity. In the top-down methods, the most well-known method is reduction of the graphene oxide. This method needs to overcome the limitation that defects occur in oxidation and reduction process. Therefore, this study focused on the synthesis and exfoliation of graphite intercalation compound (GIC) in order to pursue both high productivity and high quality. For the improvement of exfoliation efficiency, it is essential to weaken the van der Waals attraction between graphite layers. GIC was exfoliated in a familiar solvent with the intercalated material to maximize the weakening of interlayer attraction. Microwave was used as a heat source for efficient energy supply in solvent. As a result, single layer graphene is produced by very easy, simple and fast process. There was no sonication, no dispersion, no reduction and no toxicity. Also, produced graphene was water-soluble.

266

Effect of Cyclization Degree on the Iodine Adsorption Property of Stabilized Polyacrylonitrile Fibers

Zhang, L1, Liu, J1, Xue, Y1, Liang, J1, Wang, X1

[email protected]

1State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical

Technology, Chao-Yang District, Beijing 100029, China Flinders University,

The effect of cyclization degree on the iodine adsorption property of stabilized polyacrylonitrile fibers were investigated by adjusting the temperature during stabilization process. Based on the FT-IR and iodine adsorption results, the cyclization degree of PAN fibers increased first, and then decrease with increased temperature, and the iodine adsorption value followed the same trend. When the temperature was at 275 , the highest value of cyclization degree was achieved, and the highest iodine adsorption of 1700.6mg/g was realized at the same time. KEY WORDS polyacrylonitrile fiber; cyclization degree; iodine adsorption

267

Effect of (C-F)bond on AC introduced by direct-fluorination on CDI

Min-Ji Kim, Kyung Hoon Kim, Hanjoo Jo, Da Hee Kang, and Young-Seak Lee*

Department of Chemical Engineering and Applied Chemistry,

Chungnam National University, Daejeon, 34134, Korea


The capacitive deionization (CDI) is a promising desalination technology, which is based on electric double layer, because of its high energy efficiency and durability. In this study, we investigated the effect of C-F bond, which is introduced by direct-fluorination, on CDI performance. To introduce C-F bond on a surface of activated carbon (AC), the direct-fluorination is conducted at room temperature using fluorine gas and nitrogen gas with different partial pressure ratio. The cathode of CDI is prepared using pristine AC and the direct-fluorinated AC (FAC), and the anode of CDI is prepared using pristine AC. The concentration of C-F bond of the prepared AC increases, whereas specific surface area of the prepared AC decreases according to increase in the partial pressure of fluorine gas. Thus, the open circuit voltage of the FAC electrode has a tendency because C-F bond has a negative electric charge. For these reasons, the electrosorption capacity of the FAC electrode in optimized condition is 16.3 mg/g, it increases 58.3% compared to that of pristine AC electrode. This study provides a unique method to prepare highly negative charged CDI cathode and it may be helpful for the development of high performance CDI cells.

268

Effect of Carbon Fiber Microstructure on the Formation Transition Metal Carbides and the Mechanism of the Reaction of Transition Metal with Carbon Fibers

Xuanke, L1,2,3, Hui, Z1,2, Zhijun, D1,2, Fei, H3, Ye, C1,2, Guanming, Y1,2, Zhengwei, C1,2,

Aidan, W4


1The State Key Laboratory of Refractories and Metallurgy, Wuhan University of Science and Technology, Wuhan, Hubei, 430081, PR China 2Hubei Province Key Laboratory of Coal Conversion and New Carbon Materials, Wuhan University of Science and Technology, Wuhan, Hubei, 430081, PR China 3The Research Center for Advanced Carbon Materials, Hunan University, Changsha, Hunan, 410082, PR China 4School of Chemical and Process Engineering, University of Leeds, Leeds, LS2 9JT, UK

The effect of carbon source crystallite size on the formation of transition metal (Ti, Zr,

Hf) and silicon carbides coating was investigated via direct reaction of transition metal powders with mesophase pitch-based carbon fibers (CFs) heat-treated at various temperatures. X-ray diffraction, scanning electron microscopy and energy dispersive X-ray spectroscopy analyses reveal that uniform and dense transition metal carbide coatings are preferentially formed on CFs containing larger and more ordered graphite crystallites. The carbide synthesis temperature and the sizes of crystallites in the CFs have a remarkable influence on the integrity and thickness of the coatings. The formation the transition metal carbide coatings can be attributed to the surface diffusion of transition metal and the bi-directional diffusion of transition metal and carbon sources inside the HfC coating. The reaction of carbide coated carbon fibers with zirconium powders leads to the growth of ZrC on the HfC coating and this has been shown to occur by the diffusion of carbon from the carbon fiber core through the carbide coating to its surface.

269

Effect of carbon structure on Ru catalyst for ammonia synthesis

Nishi, M1, Taira, A2, Takagi, H1


1 National Institute of Advanced Industrial Science and Technology, Tsukuba, Japan 2 Tsukuba University, Tsukuba, Japan

In recent years, ammonia has attracted attention as hydrogen or energy carrier, therefore, research on ammonia synthesis process under mild condition has proceeded. It is known that Ru supported catalyst has high catalytic activity for ammonia synthesis at lower pressure and temperature. On the other hand, the catalytic activity depends on the catalytic support and supported promoter. In this work, we investigated how carbon support and promoter affect activity of Ru catalyst for ammonia synthesis. We prepared Ru catalyst changed pore structures of carbon support and the amount of supported Cs as a promoter. As a result, Ru catalyst which the supported carbon materials having lower surface area and higher crystalline graphite exhibited higher catalytic activity. Moreover, we observed higher catalytic activity when the larger amount of Cs was supported on carbons. It suggests that the electron-donating from large amount of Cs around a Ru promotes the N2 bond dissociation. These results imply the combination of carbon structure and the amount of supported Cs affect the catalytic activity of Ru catalyst for ammonia synthesis.

270

Effect of electroless Ni plating of oxyfluorinated CNT on EMI-SE

Kyeong Min Lee1, Min Jung Jung1, Hongn Gun Kim2, Seung-Kon Ryu2 and Young-Seak Lee1,*

1Department of Chemical Engineering and Applied Chemistry,

Chungnam National University, Daejeon, 34134, Korea 2Institute of Carbon Technology, Jeonju University, Jeonju, 55069, Korea

(*[email protected]) Multi-walled carbon nanotube (MWCNT) were oxyfluorinated using mixture of oxygen and fluorine gas and followed by electroless Ni plating to control amount of Ni. The effects of oxy-fluorination on surface of MWCNT were investigated by X-ray photoelectron microscopy (XPS). These raw or oxyfluorinated MWCNT were plated with nickel. These Ni plated samples were manufactured into a thin film on PI film, The amount of plated Ni and surface morphology of MWCNT were changed according to pressure ratio of oxyfluorination. The EMI shielding efficiency of the Ni plated CNT with oxygen: fluorine ratio in 1:9 exhibited a maximum value in this study. These results are attributed that oxyfluorination could be controlled the amount of plated Ni onto CNT. These Ni plating of oxyfluorinated CNTs have a great potential for EMI shielding applications.

271

Effect of electrolyte pH stabilisation on carbon-based capacitor performance

Platek, A, Piwek, J, Fic, K, Frackowiak, E



The work reports on the performance enhancement of the activated carbon-based electrochemical capacitors. Particular attention has been focused on the selection of the most suitable electrode material as well as on the influence of the electrolyte pH on the carbon electrode stability. Since the energy density of the electrochemical capacitors depends on the squared operating voltage, this work has been essentially focused on the capacitor performance at high voltage conditions. Detailed characterization of the electrochemical capacitor was done to verify the influence of the electrolyte pH stabilisation on the carbon electrode performance. As it is widely known from the literature, the adsorption of hydrogen causes the local changes of pH towards more alkaline.

<AC> + H2O + e- <AC>Hads + OH-

However, application of buffer solution with relatively weak acidic pH (5.12 at 25oC) allowed hydroxide anions to be neutralised and improved the reversibility of charging/discharging processes at higher voltages (1.5 V). Physicochemical analysis of different activated carbons allowed the most suitable active material to be selected. It has been finally proved that pore size distribution of the Kuraray YP50F activated carbon matched acetate buffer ion dimensions and demonstrated the most optimal electrochemical performance. The capacitance of carbon electrode exhibited 50 F g-1 (at 0.8 V and 5 A g-1 current load), and 76 F g-1 at 1.5 V. For in-depth study, the carbon electrode – electrolyte solution interactions have been elucidated using two- and three-electrode assembly. Long term analysis proved 100h work at constant polarisation (1.5 V) with 20% decrease of specific capacitance.

272

Effect of fluorination onto preform on high-densification of carbon/carbon composites

Do Young Kim, Ji-Hyun Kim, Kyeong Min Lee, Sangmin Lee, and Young-Seak Lee* Department of Chemical Engineering and Applied Chemistry,

Chungnam National University, Daejeon, 34134, Korea (*[email protected])

In this study, we have prepared carbon/carbon(C/C) composite from surface-treated preform with different direct fluorination. The effect of direct fluorination on the properties of C/C composite has been investigated by apparent density, real density, and X-ray photoelectron spectroscope(XPS). The cross-section of these carbon/carbon composites are also observed using polarization microscope. The apparent density of C/C composite has been differently obtained according to the partial pressure of direct fluorination. The apparent density of C/C composite have been measured to be 1.325 g/cm3 from fluorinated preform under the condition of 0.1 bar, which is showed to be increased to about 30% compared to C/C composite with the untreated preform. These results can be attributed to the variation of surface free energy by direct fluorination.

273

Effect of fluorine stabilization on carbonization yield of cellulose fiber

Kyeong Min Lee1, Min Il Kim1, Hongn Gun Kim2, Seung-Kon Ryu2 and Young-Seak Lee1,* 1Department of Chemical Engineering and Applied Chemistry,

Chungnam National University, Daejeon, 34134, Korea 2Institute of Carbon Technology, Jeonju University, Jeonju, 55069, Korea


Cellulose fibers were treated by fluorine stabilization according to reaction temperature to increase of thermal stability and carbonization yield of them. The properties of fluorine stabilized cellulose fibers were analyzed by FT-IR, XPS and TGA. The fluorine stabilized cellulose fibers were carbonized in N2 gas at 800 oC for 1h. Increasing of fluorine stabilization temperature was increased the fluorine functional group content in fluorine stabilized cellulose fibers. Initial decomposition temperature of fluorine stabilized cellulose fibers was decreased and carbonization yield was increased by increasing of fluorine functional group. The introduction of fluorine functional groups increased the carbonization yield of cellulose fibers by increasing the number of C=C bonds via the pyrolysis of fluorine functional groups during carbonization process. The carbonization yield of cellulose-based carbon fibers was increased to 52.5% compared to pure cellulose fibers by direct fluorination at 120 oC.

274

Effect of oxyfluorinated CF-powder on mechanical properties of CNT-epoxy composites

Ye Ji Choi, Kyeong Min Lee and Young-Seak Lee* Chemical Engineering and Applied Chemistry,


PAN-based carbon fiber is ground to powder (10 – 150 um), and then modified by oxygen and fluorine gas to improve the interfacial adhesion with epoxy resin. The surface properties of modified carbon fiber powder (mCFP) is investigated by X-ray photoelectron spectroscopy (XPS) and contact angle analysis (CAA). The cross-section of epoxy composites reinforced CNT and mCFP are also observed by scanning electron spectroscope (SEM). The mechanical properties of these composites are evaluated by tensile and impact test. The mechanical properties of epoxy composites reinforced CNT and mCFP in condition of oxyfluorination (O2:F2=3:7) are largely increased by respectively 38%, 21% in tensile and impact strength compare to those of CFP/CNT/epoxy composites. This results are attributed to increased interfacial adhesion between CFP and epoxy resin by enhanced polarity of the surface for oxyfluorination.

275

Effective packing method of carbon nanotube fiber through liquid infiltration

Lee, H1, Lee, T1, Lee, S.-H1, Lee, K.-H1*

[email protected]

1 Department of Chemical Engineering, POSTECH, Pohang 790-784, Korea The carbon nanotube (CNT) fiber have not yet realized the physical and electrical properties of individual CNTs due to the alignment of the internal CNT bundles and low packing density in CNT fiber. If CNT fiber can realize the properties of individual CNTs, CNT fiber is considered as a key material to lead various markets. Many physical and chemical methods such as pressing and cross-linking were introduced to improve the packing and the alignment of the CNT fiber. Liquid infiltration is one of effective way to densify the CNT fiber. In this work, we explored effective packing method of CNT fiber through liquid infiltration. In general liquid infiltration method, a CNT fiber is mainly packed during drying process by the capillary force. However, we use wicking method to apply the capillary effects to the infiltration process and drying process. The capillary force can be influenced by many variables (the surface tension, volatility, interaction, and affinity of solvents). Solvents were selected based on Hansen solubility parameter which was used to characterize the affinity between the CNT fiber and the solvent. Infiltration temperature was selected based on the viscosity of the solvent. After liquid infiltration, the strength of fiber was measured using Favimat, and the morphology was observed by SEM. DMSO was the most effective in decreasing the diameters of the CNT fibers. The tenacity of CNT fiber is increased from 0.41 (N/tex) to 0.77 (N/tex), and load is increased from 2.7 (cN) to 4.4 (cN).

276

Effective Stabilization of Isotropic Pitch Fiber Under Pressurized Atmosphere

Shimanoe H1, Tanaka S1, Kato O, Nakabayashi K1, Miyawaki J1, Yoon SH1


1 Kyushu University, Kasuga, Fukuoka, Japan

Pitch materials which contains various compositions of condensed aromatic hydrocarbons

can be used as an effective precursor for carbon fiber. However, it is considered to be very difficult to spin such a pitch material into thin pitch fiber of less than 10 µm in diameter because the molecular weight of pitch material is usually less than 1000 u. In spite of such a spinning difficulty, isotropic pitch with softening point of less than 220oC shows relatively high spinnability and can be spun into thin pitch fiber with less than 10 micro-meter of diameter. However, the isotropic pitch fiber derived from the isotropic pitch with the softening point of less than 220oC is very difficult to obtain the successfully stabilized fiber because of the fiber fusion between pitch fibers among oxidative cross-linking on stabilization. In this study, we tried to carry out the stabilization of isotropic pitch fiber which derived from

the low softening point (SP) isotropic pitch with SP= 200 and 220oC under the pressurized air-atmospheric stabilization conditions. We examined oxygen up-takes of isotropic pitch fibers (SP=200 and 220oC) among

stabilization using thermogravimetric analysis using magnetic suspension balance (MSB-TG) and carried out pressurized stabilization under 1-10 bar. The stabilization started at lower temperature and higher oxygen up-take under pressurized condition compared to atmospheric one. SEM showed less degrees of fiber fusion in the carbonized fiber which was stabilized under pressure than that of carbon fiber stabilized under atmosphere.

277

Effects of different carbon matrix on ablation behaviors of C/C-ZrC-SiC composite

Wei, S1, Yabin, C1, Xiang, X1, Yonglong, X1, Zhen, P1, Zhaoke C1, Yalei, W1

[email protected]

Central South University, Changsha, China

Porous C/C composite densified by pyrolytic carbon and resin-derived carbon respectively was infiltrated by Zr,Si molten at 2000 , and two different types of C/C-ZrC-SiC composite(PyC-C/C-ZrC-SiC composite and RI-C/C-ZrC-SiC composite) were successfully fabricated.The results show that the density of RI-C/C-ZrC-SiC composite is higher that that of PyC-/C-ZrC-SiC composite.Besides, the distribution of ceramics within RI-C/C-ZrC-SiC composite is more uniform, and most pores between carbon fibers are infiltrated by ceramics.Finally, a network structure is developed. While the ceramics in PyC-C/C-ZrC-SiC composite only distribute inside the short cut carbon fiber layers. The difference of ceramic distribution is supposed to be due to the distribution of pores and carbon matrix.The ablation test confirms that RI-C/C-ZrC-SiC composite exhibits a better ablation resistance. Both its mass and linear ablation results are lower than that of PyC-C/C-ZrC-SiC composite. In addition,the results indicate that RI-C/C-ZrC-SiC composite is able to reach a stable ablation condition when its mass and thickness show slight change during the ablation process. However, the mass of PyC-C/C-ZrC-SiC composite continues to loss with time, which indicates that this composite were suffering oxidation all the time.

278

Effects of Interfacial Bonding Mechanisms on Compressive Damage Tolerance

Stojcevski, F, Hilditch, T, Henderson, L, Naebe, M

[email protected]

Deakin University, Waurn Ponds, Australia

This project investigates the effects of sizing deposition level and electrochemical oxidization treatment on compressive damage tolerance performance within CFRP composites. Systematic testing from a singular fiber level through to composite panels looks into how fiber modifications using sizing and electrochemical treatment effect interface bonding mechanisms (namely mechanical interlocking, fiber wetting and chemical adhesion) and subsequent compressive strength. Accordingly to what degree are these modifications translatable from single fiber level to the final performance of a composite? This project is addressing the weaknesses of interfacial adhesion and clarifying the role of bonding mechanisms and fiber treatments essential for the improvement of compressive damage tolerance. Experimentally both precise characterisation of fibers and resins formats and a gradual upscaling of mechanical testing are required. Characterisations is being conducted using atomic force microscopy (AFM), dynamic contact angle testing (DCAT), Fourier Transform Infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM) and X-Ray photon spectroscopy (XPS). Accordingly mechanical testing is progressing from single fiber fragmentation testing (SFFT) through to short beam shear (SBS) to assess interface strength. Results are compared to compression after impact (CAI) testing, open hole compressive (OHC) testing and fracture toughness testing (DCB) data. A clear progression relating the effects of interfacial bonding mechanisms to fiber modification can thereby be drawn through all levels of testing providing clear insight into how sizing and electrochemical treatment can effect compressive damage tolerance in composi

279

Elastic Properties in van der Waals 2D Materials

Hwangbo, Y1, Woo, S.-J.2, Lee, C.-K.1, Son, Y.-W.2, Kim, J.-H.1


1 Korea Institute of Machinery & Materials (KIMM), Daejeon, Republic of Korea 2 Korea Institute of Advanced Study (KIAS), Seoul, Republic of Korea

Using in-situ AFM and Raman bugle tests, Grüneisen parameter (γG) and Young’s modulus (E) of graphene from monolayer to 22 layers were systematically investigated. The apparent γG and E of graphene with realistic boundary conditions were measured to decrease as the increase of the number of layers while the intrinsic ones for graphene were shown to be independent of the number of layers. The ratio of E/γG was shown to be considered as a materials constant of multi-layered graphene both for apparent and intrinsic ones, and the apparent Young’s modulus of the multi-layered graphene for the realistic applications are easily obtainable by measuring the apparent Grüneisen parameter based on the ratio. More excitingly, this behavior can be readily extended to other layered van der Waals 2D materials because the interlayer coupling in all the 2D materials is basically attributed to van der Waals interaction, and it enables us to use the ratio of E/γG as a material constant for van der Waals 2D materials as well as their 2D heterostructures. The present study will provide a powerful guide for estimation of mechanical property and variety of applications using various layered van der Waals 2D materials.

280

Electrically Conductive Transparent Films from Polyacrylonitrile (PAN) and Carbon Nanotubes

Yanqing Wang1*, Bunshi Fugetsu1, 2, Ichiro Sakata1, 2, Wei Gong1, Morinobu Endo3, Mildred

Dresselhaus4 & Mauricio Terrones5

[email protected]

1School of Engineering, The University of Tokyo, Bunkyo-ku, Tokyo 113-0032, Japan. 2Policy Alternative Research Institute, The University of Tokyo, Bunkyo-ku, Tokyo 113-


Nagano 380-8553, Japan. 4Research Laboratory of Electronics, Department of Electrical Engineering and Computer

Science, Department of Physics, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, MA 02139-4307, USA.

5Department of Physics, Department of Chemistry, Department of Materials Science and Engineering and Center for 2-Dimensional and Layered Materials, The Pennsylvania State

University, University Park, PA 16802, USA. Electrically conductive transparent films based on polyacrylonitrile (PAN) and carbon nanotubes (CNTs) have been synthesized through a facile and scale-up bar-coating method. PAN contained carbon nanotubes, being pre-dispersed into a tubular level of dispersions, were used as the starting material and the electrically conductive transparent PAN/CNT films were obtained via a template-free method. First, electrically conductive transparent films with high flexibility and continuous porous structure were established by using a temperature-induced phase separation (TIPS) method. Second, electrically conductive transparent films with a surface resistance (Ω/sq) from several hundred to tens of thousands and a uniform mesopore structure were obtained. The as-prepared flexible and robust films have potential applications in filtration, adsorption, etc. through or not further chemical modification and functionalization.

281

Electrochemical Oxidation of Carbon Xerogels And Correlation with Physico-Chemical Properties

Sebastián, D1, Alegre, C1, Gálvez, ME2, Lázaro, MJ1


1 Instituto de Carboquímica, CSIC, Zaragoza, Spain 2 University of Sorbonne, UPMC Paris, Jean le Rond D'Alembert Institute, UMR CNRS,

Saint-Cyr L'Ecole, France

Carbon xerogels (CXGs) are of great interest from a quality-to-cost point of view among the different gel-derived carbon typologies (mainly comprising also aerogels and criogels). Such advanced carbon-based materials are playing a key role nowadays in the development of low-cost and environmentally friendly electrochemical devices devoted to the conversion and storage of energy, such as fuel cells, electrolyzers, batteries, solar cells and supercapacitors. Regardless the more or less graphitic nature of carbon materials, in the presence of electron acceptor species like water, the occurrence of relatively high positive potentials (> 1 V vs. RHE) unavoidably results in a certain degree of carbon oxidation reaction (COR), and thus, the degradation and eventual modification of the electrode initial properties. The discussion about the electro-oxidation mechanism and the influence of carbon characteristics is still an open question, even though it is known that high a graphitic character and a low surface area help to reduce the oxidation rate. CXGs, though possessing a certain ordering degree in the short-range, are not graphitic materials. This fact, together with their relatively highly developed porosity, make them more prone to corrosion processes than graphite-like carbons. The main scope of the present work is to investigate the electro-oxidation behaviour in acidic solution of CXGs differing in porosity and surface chemistry. The control of some specific CXGs features like the surface chemistry and carbonization conditions appears of paramount importance to design strategies to minimize degradation phenomena related to carbon electro-oxidation.

282

Electrochemical Performance of Carbons Prepared by Chemical Activation of

Biomass

Pavlenko, V1,2, Abbas Q3, Prikhodko N1,4, Biisenbayev M1, Tuleibayeva A1, Béguin F3, Mansurov Z1,2



2 Al-Farabi Kazakh National University, Almaty, Kazakhstan 3 Poznan University of Technology, Poznan, Poland

4 Almaty University of Energetics and Communications, Almaty, Kazakhstan

During the discussion, the chemical conversion of biomass wastes into the high quality activated carbons (ACs) with capacitance performance will be presented. The application in electrochemical capacitors of electrode composites prepared on a base of the micro-mesoporous carbons derived through the one step activation of walnut shells (WS) impregnated with phosphoric acid has been investigated for the first time. The activation of the impregnated WS precursor was performed over a wide range of temperatures producing a good yield of hard carbons with well-developed porous texture. ACs derived from the WS were characterized by means of low temperature nitrogen adsorption, scanning electron microscopy, energy-dispersive X-ray spectroscopy and various electrochemical techniques. Activated carbons prepared in the temperature range of 350 °C to 800 °C exhibited the highest BET specific surface area of approximately 2300 m2 g-1 and a total pore volume up to 1.60 cm3 g-1 calculated by non-local density functional theory (NLDFT). It was found that the activation temperature equal to 800 °C leads to formation of ACs with high specific surface area and increased volume of micropores. When implemented in symmetric supercapacitor cells using 1 mol L-1 Li2SO4 aqueous electrolyte, the ACs obtained from H3PO4-impregnated WS activated at displayed a capacitance values of 190-200 F g-1 (per mass of one electrode)

283

Electrochemical Response of Biomass Waste Activated Carbon in Polymer-Gel

Electrolytes

Momodu, D1, Bello., A1, Oyedotun, K1, Ugbo, F,1, Madito, M,1, Barzegar, F1, Dangbegnon J,1 and Manyala, N1


1Department of Physics, Institute of Applied Materials, SARCHI Chair in Carbon Technology and Materials, University of Pretoria, Pretoria 0028, South Africa.

Activated carbon (ACB) obtained from a tree bark waste biomass was obtained by adopting an optimized activation and carbonization route using potassium hydroxide (KOH) pellets. The morphological and structural characteristics of the optimized carbon material revealed a porous network suitable for charge storage. The potential of the ACB material as a suitable supercapacitor electrode was investigated in a symmetric two electrode cell configuration using a polymer-gel/KOH active electrolyte. The KOH was included to improve ionic mobility within the polyvinyl alcohol (PVA) gel, while carbon acetylene black and polymer-fullerene blend acted as the conductive additives. The cell exhibited an EDLC behaviour in all electrolytes with the PVA/KOH /carbon black (PKC) electrolyte portraying an improved electrochemical response within a 1.4 V voltage window. A specific capacitance (CS) of ∼227 F g-1 was obtained with a corresponding energy density of 15.5 W h kg-1 and power density of 700 W kg-1 at a current density of 0.5 A g-1. An excellent stability was exhibited with a coulombic efficiency of a 97.5% after 5000 continuous cycling at 5.0 A g-1 and a slight deterioration of the ideal electrochemical behavior was observed after further subjecting the electrode to floating test for 120 h (5 days) at 1.4 V. Interestingly, the gel-based electrolyte showed a peculiar “recuperating behaviour” after further floating process which demonstrates the viability for adopting gel-electrolytes in SC devices from plant biomass waste.

284

Advantages of Emploing Oxygen Adsorption For The Chracterization Of Carbon Nanopore Structure

Jagiello, J, Kenvin JC [email protected]

Micromeritics Instrument Corporation, Norcross, GA, USA

The pore structure of porous carbons is usually characterized in terms the pore size distribution (PSD) most often derived from the analysis of standard nitrogen and argon adsorption isotherms measured at their boiling temperatures (77, 87 K). From the two gases argon is recommended [1] as more reliable for the PSD analysis because of its minimal specific interactions with the surface chemical groups. Such interactions may influence adsorption of nitrogen molecules that possess a significant quadrupole moment and thus may interact specifically with the surface polar groups.

Unfortunately, using liquid argon as a cryogen for argon adsorption measurements may be challenging due to its high cost and a limited availability in various parts of the world.

In this work, we propose using adsorption isotherms of oxygen for the PSD characterization of porous carbons. Oxygen has the quadrupole moment about 3.5 times lower than nitrogen and thus the possible effect of polar surface sites is much smaller on the isotherms of oxygen than nitrogen.

Oxygen has a wide liquid-vapor coexistence curve (54-154 K) that allows for using various cryogenic baths including standard liquid nitrogen. We demonstrate a quantitative agreement between the PSD results obtained from the isotherms of Ar measured at 87 K and O2 measured at 77 K on selected microporous carbons. The data were analyzed using 2D-NLDFT [2] models (kernels) developed for these gases and temperatures.

References [1] Thommes, M. et al. Pure and Applied Chemistry 87, 1051-1069 (2015). [2] Jagiello, J. & Olivier, J. P. Carbon 55, 70-80

285

Enhanced Na storage performance by rational design of SnO2/nanocarbon composites

Cui, J, Yao, S, Kim, J.K.


Department of Mechanical and Aerospace Engineering Hong Kong University of Science and Technology, Hong Kong SAR, P. R. China

SnO2 is a cost-effective and non-toxic material, and has been extensively used as anode for Na-ion batteries (NIBs). However, it suffers poor electron/ion conductivities and a large volume change, resulting in limited rate performance and rapid capacity fade. To address these issues, highly conductive and mechanically robust nanocarbons, such as graphene and carbon nanotube (CNT), are used to form a porous SnO2/carbon composite. Graphene and CNTs can serve as conductive matrix to enhance the conductivity and mitigate the volume change. The porous nanostructure can further facilitate the penetration of electrolyte and accelerate the Na+ ion diffusion process. We synthesize two types of SnO2/nanocarbon composite anodes for NIBs, namely, the SnO2/CNT core-shell structured anode (SnO2/CNT) and SnO2/Graphene-CNT aerogel anode (SnO2/GCA). The strong interaction between SnO2 and CNTs endows the composite with greatly enhanced reaction kinetics, which in turn gives rise to remarkable reversible specific capacities of 630.4 mAh g-1 at 0.1 A g-1 and 324.1 mAh g-1 at a high current density of 1.6 A g-1 for SnO2/CNT. The SnO2/GCA electrode delivers a better cyclic stability with 74 % capacity retention after 500 cycles due to the uniform distribution of SnO2 nanoparticles on the porous aerogel structure. References: [1] J. Cui, S. Yao, J.K. Kim, Energy Storage Mater. 3 (2017) DOI: 10.1016/j.ensm.2016.12.005 [2] S. Yao, J. Cui, Z. Lu, Z.L. Xu, L. Qin, J. Huang, Z. Sadighi, F. Ciucci, J.K. Kim, Adv. Energy Mater. 7 (2017) 1602149. [3] J. Cui, Z.L. Xu, S. Yao, J. Huang, J.Q. Huang, S. Abouali, M. Akbari Garakani, X. Ning, J.K. Kim, J. Mater. Chem. A 4 (2016) 10964–10973.

286

Enhancement of Mechanical Properties of CFRTP Using Polymer Colloids

Uematsu, K, Yamamoto, T, Irisawa, T

[email protected]

Nagoya University, Nagoya, Japan

This study showed the development of technique to enhance the mechanical properties of carbon fiber reinforced thermoplastic (CFRTP) using nylon by improving the resin impregnating property and the interfacial adhesion between the carbon fiber and the resin. The nylon particles in the polymer colloids were adsorbed on the carbon fiber using electrophoresis. The amount of nylon particles adsorbed on the carbon fiber was able to be controlled changing the applied voltage in the electrophoresis for a short time. The interfacial adhesion between the modified carbon fibers and the thermoplastic resin was measured. As a result, it was confirmed that an improvement of 60% or more. It shows that the interfacial adhesion of CFRTP can be controlled by combining basic techniques, such as preparation of polymer colloid and electrophoresis operation. Furthermore, the interfacial shear strength between the carbon fiber and the resin was controlled by the present method. In this process, it is important to make the resin into fine particles. And this method was a basic technique for making CFRTP with high performance. Since this method can be applied to highly versatile thermoplastic resin, CFRTP with high performance are expected to be used for automotive lightening.

287

Enormous removal of acetaldehyde using aniline supported cellulose-based

activated carbon fiber

Ryu DY1, Shimohara T2, Nakabayashi K1,2, Miyawaki J1,2, Yoon SH1, 2.*


1 Interdisciplinary Graduate School of Engineering Science Kyushu University, Kasuga, Japan

2 Institute of Materials Chemistry and Engineering Kyushu University, Kasuga, Japan

Gaseous acetaldehyde (CH3CHO), one of the major sick-house gasses, would cause

serious health problems. Therefore, efficient removal of CH3CHO is strongly required for the indoor environmental improvement. We herein reported a development of an efficient adsorbate for removing CH3CHO using the cellulose-based activated carbon fiber (ACF) on which aniline was impregnated. Aniline was impregnated using aniline-ethanol solution. The CH3CHO removal performance was closely examined using self-designed continuous flow measurement apparatus with 2 ppm of CH3CHO balanced with N2/O2 (79/21, v/v) at a total flow rate of 100 ml min-1 as an inlet gas for 0.05 g of each ACF sample. It was found that the supported aniline can afford the effective removal of the low-concentrated gaseous CH3CHO regardless of humidity in the atmosphere. Through the optimization of the impregnation amounts of aniline, the removal performance of CH3CHO drastically increased to longer than 165 h of the breakthrough time, whilst the breakthrough time of ACF without aniline impregnation was only 30 min.

288

Estimation of carbonization and activation yields by a predictive calculation

Belot, G1, Cagnon, B1, Roulet, M1, de Persis, S2, Charpentier, J.P3, Pineau, A1, Bonnamy, S1,*


1 CNRS, Univ. Orléans, ICMN UMR 7374, F-45071 Orléans, France 2 CNRS, ICARE UPR 3021, F-45071 Orléans, France

3 INRA Val de Loire, UR AGPF 0588 et plateforme GénoBois, F-45075 Orléans, France

The control of the activation yield and of the activated carbon porous texture requires the control of each stage of the activation procedure and the knowledge of the raw lignocellulosic materials composition. In the case of chemical activation, the economic and environmental constraints force to decrease as well as possible the quantities of activating agent, of energy and waters used. This can be carried out by optimizing the thermal treatment. The study of the lignocellulosic residues requires the knowledge of the raw material (chemical composition, elemental analyses…). The study of the experimental parameters is not sufficient to control pyrolysis and combustion gases as well as the final solid material obtained after the heat treatment. The objective of the study is to optimize the heat treatment of chemical activation procedure by H3PO4 of lignocellulosic precursors (miscanthus, olive pomaces, tomatoes plant and poplar wood). The contents of hemicelluloses (H.), cellulose (C.), and lignin (L.) were determined for each sample. The TGA analyses were carried out on all the lignocellulosic precursors and on artificial mixtures of the three pure compounds (H., C., L.) to estimate their respective contribution in the final mass of the activated carbons to establish the predictive calculation. The microporosity of activated carbons was characterized by nitrogen adsorption at 77 K. The predictive calculation was established using the experimental results to evaluate the carbonization and activation yields and the respective contributions of H., C., L. to the activated carbons in term of weight fraction. These equations were validated.

289

Fabrication of carbon fiber reinforced steel composites using SPS

Gayoung Kim1, Minchang Sung1, Woong-Ryeol Yu1


1 Department of Material Science and Engineering and Research Institute of Advanced Materials (RIAM), Seoul National University, Seoul, Korea

Due to its excellent strength, hardness, and ductility, steel has been used for variety engineering applications. Steady research has been carried out to improve specific strength of steel for lightweight applications to transport vehicles. Carbon fiber reinforced steel (CFRS) can be considered as a perfect candidate for this, however various hurdles should be overcome. Most serious problem is process temperature. Steel has high melting temperature (1500 ) while carbon fibers can be oxidized at such a high temperature. As such, carbon fiber reinforced metal matrix composites have been researched for metals with low melting temperature, such as magnesium and aluminium. On the other hand, short fiber reinforced metal matrix composites were fabricated by powder metallurgy that can reduce processing temperature, e.g., CNT or ceramic fibers were used as reinforcement of metal matrix composites. In this research, a fabrication method of steel composites reinforced by long carbon fibers is researched using steel powders, continuous carbon fibers, and spark plasma sintering (SPS). Pressure and pulsed current in SPS increases heating rates and reduces time and temperature for sintering, leading to the consolidation of CFRS at relatively low temperature without excessive grain growth and with less damage on carbon fibers. Microstructure and mechanical properties of CFRS will be investigated systematically and presented at the conference.

290

Fabrication of large-sized bamboo-shaped carbon nanotubes bulk materials

L. Guo, G. Kou


State Key Laboratory of Solidification Processing, Carbon/Carbon Composites Research

Center, Northwestern Polytechnical University, Xi'an, China

Though large-sized high density bulk isotropic pyrocarbon materials were prepared by fixed-bed chemical vapor deposition, it composed of highly graphitized spherical nanoparticles tightly wrapped by tangled ribbon-like pyrocarbon. There was no continuous reinforcement in bulk isotropic pyrocarbon materials. Based on the theoretical research on isotropic pyrocarbon materials and carbon nanotubes, we designed to use carbon nanotubes to strengthen isotropic pyrocarbon materials. The preliminary result showed that large-sized (65 mm × 15 mm × 15 mm) bamboo-shaped carbon nanotubes (CNT) bulk materials were fabricated by thermal gradient chemical vapor deposition by combining the growth of CNT and the formation of pyrolytic carbon together, and copper played as catalytic to catalyze the growth of CNT. Its density and porosity was about 1.77 g/cm3 and 0.4%, respectively. The diameter of CNT was different from 0.1 μm to 20 μm, most of them showed bamboo shape. They intertwined with each other intricately in CNT bulk materials, and it could make the bulk material show isotropic properties. And the CNT bulk materials showed excellent flexural strength (> 160 MPa) and compression strength (> 380 MPa) after heat treatment at 2450 .

291

Fabrication of Patterned CVD-graphene Using Imprint Technique under Room Temperature

Sang-Min Kim1,3, Bongkyun Jang3, Kyungmin Jo2, Donghyuk Kim1,3, Jihye Lee3, Kyungshik

Kim3, Seung-Mo Lee3, Hak-Joo Lee3, Seung Min Han1, Jae-Hyun Kim3


1 Korea Advanced Institute of Science & Technology, Daejeon, Korea 2 Korea Research Institute of Standards and Science, Daejeon, Korea

3 Korea Institute of Machinery & Materials, Daejeon, Korea

Chemical vapour deposited (CVD) graphene has been regarded as one of promising candidates for transparent and flexible electrodes because of its excellent electrical, optical and mechanical properties. To be adopted for commercial applications, the CVD-graphene should be transferred on flexible polymeric substrates with large area, low cost, and high speed, and a lot of researchers have reported roll-to-roll (R2R) solutions for CVD synthesis of graphene, etching-out of catalyst metals, and graphene transfer. Addition to these R2R solutions, many applications of CVD-graphene require patterning techniques, but there are few studies on the patterning techniques of graphene compatible with R2R process.

In this study, we introduce a patterning technique of CVD-graphene with R2R compatibility, and demonstrate its capability of patterning from nanoscale donut patterns to microscale line patterns under room temperature. This patterning technique is a derivative of nano imprint lithography (NIL) and relies on the softening mechanics of catalyst metals during CVD synthesis of graphene. Mechanical analysis of the patterning technique is presented based on finite element analysis and in-plane transparent supercapacior is demonstrated based on the proposed technique.

292

Facile Synthesis of In-plane Graphene Micro-supercapacitor Using Flash Reduction

Kang, S. H.1, Hong, S. H.1, Kim, I. G.1, Kim, B. N.1, Sul, J. H1, You, I. K. 1*

[email protected]

1 Electronics and Telecommunications Research Institute, Daejeon, Korea

Here we present a simple fabrication method of in-plane graphene micro-supercapacitor using flash light irradiation. Flash light reduction of graphene oxide (GO) is an efficient method of producing high quality reduced graphene oxide (rGO) in room temperature ambient conditions without the help of hazardous reducing agents (e.g. hydrazine, hydrogen iodide). The entire process is low cost and is capable of large scale fabrication. By carefully optimizing the photo-thermal reduction conditions and utilizing shadow mask in a similar manner as for photolithography, all-carbon, monolithic supercapacitor with interdigital finger structure can be fabricated in a simple irradiation step that occurs in less than one second. The thickness of the entire fabricated device is less than a hundred micrometer, making the device highly flexible and thus very useful for variety of applications, including portable and wearable electronics. The as-formed supercapacitor benefits from the in-plane structure, which allows full utilization of high surface area of graphene layers and rapid electrolyte diffusion that results in high energy and power densities.

293

Facile synthesis of water-soluble graphene quantum dots/graphene oxide composites for efficient photodetector

Gupta, S1,*, Walden, J2

* [email protected]

1 Department of Physics and Astronomy and Advanced Materials Institute, Western

Kentucky University, Bowling Green, KY 42101, USA 2 Department of Electrical Engineering, Western Kentucky University, Bowling

Green, KY 42101, USA

Graphene quantum dots (GQDs) are a kind of 0D material with characteristics derived from both graphene and carbon dots (CDs). Combining the structure of graphene with the quantum confinement and edge effects of CDs, GQDs possess unique properties. Intense research activity in GQDs is attributed to their novel phenomena of charge transport and light absorption/ emission. The optical transitions are known to be available up to 6 eV in GQDs, applicable for photonics and biomedical technologies. We present a facile hydrothermal method for synthesizing uniform sized GQDs with a strong greenish and violet blue emission at ~ 10-14% quantum yield. This approach enables a large-scale production of aqueous GQD solution without the need for stabilizers. The structure and emission mechanism of the GQDs have been studied by combining extensive characterization techniques and rigorous control experiments. We further demonstrate the distinctive advantages of such GQDs as high-performance photodetectors (PDs). We report high-efficient photocurrent (PC) behaviors consisting of multilayer GQDs sandwiched between monolayer graphene sheets. The observed unique PD characteristics prove to be dominated by the tunneling of charge carriers through the energy states in GQDs, based on bias-dependent variations of the band profiles, resulting in novel dark current and PC behaviors. We gratefully acknowledge financial support from NSF-DMR, NSF KY EPSCoR, NASA KY EPSCoR and WKU Research Foundation grants.

294

Fiber Li-Ion Battery Based on Carbon Nanocomposite Electrode Yarns

Sarang Park1, Tae-Hyung Kang1,2, In-Suk Choi2, Woong-Ryeol Yu1


1 Department of Material Science and Engineering and Research Institute of Advanced Materials (RIAM), Seoul National University, Seoul, Korea

2 High Temperature Energy Materials Research Center, Korea Institute of Science and Technology, Seoul, Korea

Due to high energy density, long cycle life, and low memory effect, lithium ion (Li-ion) battery has been commonly used in portable devices. Recently, flexible Li-ion battery has been researched vastly for its applications to wearable electronic devices. Fiber-shaped battery can provide flexibility and formability as well as weavability, being considered as an ideal structure for wearable energy storage. In this study, fiber-shaped Li-ion battery was manufactured using carbon nanocomposite yarns and electrochemically characterized including its flexibility. Electrode materials, such as silicon (Si) and lithium iron phosphate (LFP), were electrospun with poly(acrylonitrile) (PAN) into nanofibers, which were spun again into yarns. Carbon nanocomposite yarns were finally manufactured by calcination process. Electrode yarns were coated with polymer electrolyte and assembled into a full-cell. Electrochemical tests were carried out using charge/discharge test, cyclic voltammetry, and electrochemical impedance spectroscopy. Mechanical and combined electrochemical tests were also carried out to investigate the feasibility of using fiber-shaped Li-ion battery for wearable electronics. Detailed results and discussion will be presented at the conference.

295

Finding Applications for Porous Monolithic Carbon/Carbon Composite Materials With Unidirectionally Penetrating Channels

Zheng-Ze Pan1, Wei Lv1, Hirotomo Nishihara2, Feiyu Kang1, Quan-Hong Yang1,3

Presenting author’s e-mail: mailto:[email protected]

1 Graduate School at Shenzhen, Tsinghua University, Shenzhen, China 2 Tohoku University, Sendai, Japan

3 Tianjin University, Tianjin, China Porous carbon monoliths have been emerging as a class of materials that are of particular interests to multidisciplinary fields. Most representative are fields such as adsorption, catalysis, sensing, and energy storage. Recently we have been focusing on constructing porous carbon/carbon composite monoliths with unidirectionally penetrating channels. These monoliths behaves anisotropically when it comes to its macroscopic properties. We have been making efforts on utilizing such materials in different fields. By taking advantage of the unidirectionally penetrating channels, we have constructed a new type of strain sensor by flowing gas through and checking the pressure drop that was involved in the process at the same time. Also we tried to utilize such kind of material as a free standing current collector in the field of energy storage, by which a “layer-by-layer” structure helps facilitate the electron and ion transfer, thus leading to a remarkable electrochemical performance.

296

First principles calculation of self-diffusion in graphite

M. I. Heggie1, C. D. Latham1, T. Trevethan2, P.R. Briddon3, M. J. Rayson3


1 University of Loughborough, Loughborough, United Kingdom 2 University of Surrey, Guildford, United Kingdom

3 Newcastle University, Newcastle upon Tyne, United Kingdom

The excellent review of point defect behaviour by Thrower and Mayer in 1978 [1] summarised the experimental and theoretical evidence for diffusion in graphite and how it occurred. They concluded that diffusion in graphite is by two mechanisms: Frenkel defect diffusion and an interstitialcy mechanism. Brian Kelly in ‘The Physics of Graphite’ wrote that a case can be made that maybe true self-diffusion in graphite has not been observed [2]. The observations both were made prior to the modern era of first principles calculation. Our own energy landscapes for interstitial motion based on either the Local Density Approximation or the Generalized Gradient Approximation, we show how these statements could be true, whereas other conclusions are not. We also show how the seemingly definitive calculations [3] using a van der Waals density functional [4] might also reach this conclusion while not matching all the experimental facts. [1] Thrower, P.A. and Mayer, R.M. (1978). Point defects and self-diffusion in graphite.

Phys. Stat. Sol. (a), 47, 11-37. [2] Kelly, B. T. (1981). Physics of Graphite. Applied Science Publishers Ltd, Barking, UK.

ISBN 0-85334-960-6. [3] Gulans, G., Krasheninnikov, A.V., Puska, M.J. and Nieminen, R.M. (2011). Bound and

free self-interstitial defects in graphite and bilayer graphene: a computational study. Phys. Rev. B, 84, 024114.

[4] Dion, M., Rydberg, E., Schröder, E., Langreth, D.C. and Lundqvist, B.I. (2004). Van der Waals density functional for general geometries. Phys. Rev. Lett., 92, 246401.

297

Flexible Free-Standing Graphene /Hollow Tin Dioxide Paper for Lithium-Ion Batteries

Wanyuan Zhi, Tao Xu, Qinghan Meng*, Bing Cao e-mail: [email protected]

1(College of Materials Science and Engineering, Beijing University of Chemical

Technology, Beijing 100029, China) With the appearance and development of mobile electronic devices with deformation function, the deformable and flexible lithium-ion batteries for their power supply have been paid more and more attention in recent years. In this study, a novel forming method were introduced to prepare free-standing graphene/ tin dioxide doping paper anode for lithium-ion batteries via a facile one-step physically method and the following freeze-drying and pressing. Graphene has a very high electrical conductivity and flexibility; it can be used as self-standing lithium-ion battery anode material all by itself. Hollow structure tin dioxide creates a rapid lithium transportation path and stable structure during charging and discharging. The novel structure was characterized by SEM, XRD methods, and the electrochemical performance was characterized by constant current charge and discharge, CV, EIS methods. The results show that the novel materials deliver a high discharge capacity of 930.5mA h g-1 at a current density of 100 mA g-1, even after 100 cycles there is still keep 548.2 mA h g-1 when used as binder-free lithium ion battery anode. This self-standing paper with no binder or current collector has a certain mechanical strength that can be bended as an angle. The materials provide the possibility for future flexible energy storage devices.

298

Fluorinated activated carbons as electrode materials for asymmetric capacitors

Hanjoo Jo, Kyung Hoon Kim, and Young-Seak Lee*

Department of Chemical Engineering and Applied Chemistry, Chungnam National University, Daejeon, 34134, Korea


Activated carbons (ACs) are fluorinated and prepared to electrode to investigate the fluorination effect on desalination performance of asymmetric capacitor. Changes in the surface chemical properties and pore structure of the fluorinated ACs are measured by N2 adsorption at 77 K and X-ray photoelectron spectroscopy (XPS) analysis, respectively. The electrochemical properties are also evaluated by cyclic voltammetry (CV). The desalination performance of asymmetric capacitor assembled by an untreated AC electrode as the anode and a fluorinated AC electrode as the cathode (ER||EF-) and the symmetric capacitor assembled by a pair of AC ones (ER||ER) is estimated by desalination tests. The salt adsorption capacity and charge efficiency of the ER||EF- are increased from 10.7 mg/g and 0.57 to 12.6 mg/g and 0.74, respectively, compared with the ER||ER at applied voltage of 1 V. These results are attributed that fluorinated AC electrodes have a cation attractive effect caused by the partially negatively charged fluorine-functional groups on the AC surfaces.

299

Formation of Quasi-Free-standing Epitaxial Graphene on SiC(0001) by Microwave Annealing

Kwan-Soo Kim1, Goon-Ho Park1, Hirokazu Fukidome1, and Maki Suemitsu1


1 Research Institute of Electrical Communication, Tohoku University, 2-1-1 Katahira, Aobaku-ku, Sendai, Miyagi 980-8577, Japan

Among various synthesis methods of graphene, epitaxial growth of graphene on SiC substrate is quite promising for electronic applications since it provides a high quality graphene with a large-scale-compatible, transfer-free manner. In monolayer epitaxial graphene (mono-EG) on SiC(0001), however, the carrier mobility is substantially degraded due to the phonon scattering in the buffer layer. Since one third of the C atoms in the buffer layer has a covalent bonding with the Si atom of the SiC substrate, various intercalation-based techniques have been reported to decouple the buffer layer from the SiC substrate to create a quasi-free-standing epitaxial graphene (QFSEG), but with a generation of defects and unwanted reactions of the intercalated atoms. In this paper we report a novel method to obtain QFSEG using a microwave annealing (MWA) in air. The MWA was carried out using a home-use microwave oven. Low energy electron diffraction (LEED), after MWA, indicated a disappearance of the (6√3×6√3)R30o pattern, a fingerprint of the buffer layer. The full width at half maximum (FWHM) of the Raman G’-band increased from ~33 cm-1 to ~65 cm-1 after MWA, indicating formation of a bilayer graphene. Angle-resolved photoelectron spectroscopy (ARPES) and Hall measurement indicated that the doping type changed from n-type (1.2×1012 cm-2) to p-type (1.0×1013 cm-2) after MWA. From these results, we conclude that the mono-EG on the SiC(0001) can be easily decoupled from the substrate by MWA in air, with the mono-EG being converted into a bilayer QFSEG without the buffer layer.

300

From hydrosolubility to superhydrophobicity of electrospun fluorinated nanocarbons/PVP composite films

Zha, J1 Dubois M1, Batisse N1, Claves, D1



Electrospinning appears as a powerful, simple and practical one-step method to generate continuous ultrathin fibers with micrometer and sub-micrometer diameters from a variety of polymeric materials. Most fluoropolymers are too insoluble to use in electrospinning. Usually, the strategies to prepare superhydrophobic film via such a route consist in the combination of fluorinated compounds with soluble polymers in the form of fluoro side groups or copolymers. On the contrary, we investigate a route using a hydrophilic conventional polymer such as polyvinylpyrrolidone (PVP) and addition of fluorinated nanocarbons (F-NanoC) as fllers. The resulting F-NanoC/PVP nanocomposite was prepared as a microfibrous film via electrospinning. Because the polymer matrix covered the hydrophobic fillers, the microfibrous films are hydrosoluble at this step. A post-fluorination using F2/N2 gaseous mixture was carried out. In addition to the covalent grafting of fluorine atoms on the polymer, fluorination results in its partial decomposition; the fillers emerge from this etching. Two scales of structuring are then obtained, i.e. micrometric thanks to the electrospinning and nanometric due to the emergence of fluorinated fillers. Two types of nanocarbons were investigated, namely spherical fluorinated carbon blacks (with 50 nm average diameter and CF0,9 composition) and fluorinated carbon nanofibers (160 nm, CF0,8) in order to highlight the effect of additional nano-structuring. Combination of this two-scale structuring and presence of F atoms on both polymer and fillers allows the superhydrophocity to be reached starting from a hydrosoluble nanocomposite. The water contact angle was stable for long time at 153° in the best case (nanofibers).

301

Functionalization of Graphene with Metal Particles by Thermal Methods

Prikhodko, N1,2, Temirgaliyeva, T1,3, Rakhimzhan, N1, Lesbayev, B1,3, Nazhipkyzy, M1,3, Smagulova, G1,3, Mansurov, Z1,3




For the synthesis of graphene with surface characteristics required for each specific application (for example, having a high affinity for the polymer matrix nanocomposites and good biocompatibility in sensor) is hold modification of graphene. The term "modification" means the graphene coating layers of organic and inorganic substances, or decorating the surface of graphene nanoparticles of different nature. The functionalization of carbon nanomaterials is an essential manipulation in creating materials with improved surface and bulk properties. This allows us to solve a number of pressing problems in materials science industries, electrochemistry and catalysis by creating multifunctional nanostructures consisting of graphene and nano-sized components with desired electronic and catalytic properties. There are two basic approaches to change graphene surface to impart desirable properties: covalent attachment of functional groups; non-covalent chemical compounds graphene surface by means of van der Waals, electrostatic, or p-electron interactions. In this paper was presented the results for obtaining functionalized graphene samples by thermal treatment at temperatures of decomposition of inorganic salts containing metals. The morphological and structural properties of graphene samples functionalized metallic particles of Fe, La, Ni were investigated. Structure and morphological properties of graphene, functionalized by metal particles were analyzed by the scanning electron microscope (Quanta 3D 200i Dualsystem, FEI), on Raman spectrometer (NTEGRA Spectra Raman, λ = 473 nm). The elemental composition was determined at the energy-dispersive x-ray spectroscopy (EDAX). X-ray analysis on the device "Focus M4" was held for the qualitative and quantitative analysis of the graphene samples with metal particles. Established that graphene samples were functionalized with metal particles Fe, La, Ni (35, 77, 50%) which are mainly adsorbed at the edges of the graphene. It was shown that during heat treatment formed a stable composition containing the graphene on the surface of the metal particles.

302

Graphene Oxide Film Fabrication with Controlled Thickness on Silicon-Based Substrates

Sanchez, P1, 2, Kandjou, V1, Hernaez, M1, Zamarreño, CR2, 3, Arregui, FJ2, 3, Mayes, AG1,

Melendi-Espina, S1


1University of East Anglia, Norwich, United Kingdom 2Universidad Pública de Navarra, Pamplona, Spain

3Institute of Smart Cities, Pamplona, Spain

Carbon-based films have attracted considerable attention due to their potential applications, ranging from durable nanoelectronics to efficient gas sensors and solar cells. In this regard, the outstanding mechanical and electrical properties of graphene, combined with its excellent optical transparency, offer a huge potential in the fabrication of thin, strong and efficient coatings. However, the progress in the high-yield production of graphene with specific properties is the critical step in bringing graphene applications to market. Owing to the production scalability and the convenience in processing, graphene oxide (GO) has now become an important precursor for the fabrication of graphene-based thin films. In fact, for several applications, the properties of GO are good enough and therefore its reduction is not required. Among the broad range of available deposition techniques, dip coating is an effective method of fabricating good quality thin films. Low cost, simplicity in operation and coating uniformity are key advantages of this method. Additionally, dip coating enables the fabrication and up scaling to mass production of complex, large surface area films. In this work, the dip coating technique was used to fabricate graphene oxide films. The deposition process and, consequently the film thickness, was controlled by adjusting the immersion time and the number of immersion dips. This study and experimentation also demonstrate the significance of the interlayer used to aid the adhesion of GO to specific substrates. The morphological characteristics of the obtained films were also determined by means of AFM, SEM and water contact angle measurements.

303

Graphene Supported Rhodium N-Heterocyclic Carbene Complexes as Water Oxidation Catalysts

Pérez-Mas, AM1, Álvarez, P1, Fernández-García, L1, Sánchez, B2, Gonzalez, Z1, Blasco,

J3, Pérez-Torrente, J2, Jiménez, V2, Menéndez, R1

[email protected]

1Instituto Nacional del Carbón, INCAR-CSIC, Oviedo, Spain 2 Departamento de Química Inorgánica, Instituto de Síntesis Química y Catálisis

Homogénea-Universidad de Zaragoza, ISQCH-CSIC, Zaragoza, Spain 3Instituto de Ciencia de Materiales de Aragón-Universidad de Zaragoza, ICMA-CSIC,

Zaragoza, Spain Water splitting has become an alternative pathway to store intermittent sun and wind energy contributing to mitigate the increasing global energy demand. The complexity of the removal of four electrons and protons from water makes the development of water oxidation catalysts (WOCs) a major challenge in the field. WOCs catalysts based on homogeneous Ru, Ir and Rh complexes are among the most successful. Furthermore, one of the most convenient strategies to improve their efficiency is via their immobilization at the interface of supporting electrodes. Of particular importance are those electrodes based on graphene, since they supply additional advantages (i.e. high conductivity). In this work, we report the first two examples of Rh(I) NCH-carbene complexes covalently attached to the C sp2 structure of thermally reduced graphene oxides (TRGO) as electroactive WOCs. They differ in the nature of the ligands attached to the metal centre ([RhI(CO)2((CH3)Im(C6H4))-TRGO] (TRGO-1-Rh) and [RhI(COD)((CH3)Im(C6H4))-TRGO] (TRGO-2-Rh)). Their structure and covalent attachment to TRGO were confirmed by means of XPS, Raman, thermogravimetric analysis and XAFS. Their electrocatalytic water oxidation activity and stability were studied by means of cyclic voltammetry (CV) and chronoamperometry (CA) measurements performed in a Teflon three-electrode cell in a PBS solution at pH 7 and recorded between 0.0 – 1.5 V (vs Ag/AgCl/3.5 M KCl). Although both samples are active as WOCs, TRGO-2-Rh electrode shows the highest oxidation current density. Additionally, its overpotential is lower, evidencing the beneficial effect of the donor-acceptor ligands in the metal centre to the catalysis.

304

Graphene/Nafion Composite for Fuel Cell Applications

Cunning, BV1, Bayer, T2, Ruoff, RS134, Lyth, MS2


1 Center for Multidimensional Carbon Materials, Institute for Basic Science, Ulsan, 44919, Republic of Korea

2 International Institute for Carbon-Neutral Energy Research, Kyushu University, Fukuoka, Japan

3 Department of Chemistry, Ulsan National Institute of Science and Technology, Ulsan, 44919, Republic of Korea

4 School of Materials Science and Engineering, Ulsan National Institute of Science and Technology, Ulsan, 44919, Republic of Korea

Proton exchange membrane fuel cells (PEMFCs) should ideally operate at temperatures above 100 °C. At these operating temperatures, the kinetics of the oxygen reduction reaction is increased, tolerance to fuel impurities are improved, and water and thermal management are simplified. Graphene, a single layer of sp2-hybridised carbon, has been shown to be stable in oxidizing environments up to 200 °C, impermeable to hydrogen gas, and more recently, have been found to allow proton transport through the plane. These properties make graphene potentially an ideal material in PEMFCs. Here we present a composite graphene membrane based on a single layer of graphene sandwiched between two thin layers of Nafion. At elevated temperatures and humidities, the graphene/Nafion composite was found to possess through-plane proton conductivities similar to pure Nafion. We also have found that the composite material has improved gas barrier properties compared to pure Nafion films. This work was supported by IBS-R019- D1.

305

Graphene-Based Coating for Enhanced Mechanical Properties and Radiation Performance

Li, X1, Huang, X2, Liu, Z1, Kong, Q1, Xie, L1, Su, F1, Gao, Y1, Huang, X1, Lei, H1,Guo, X1,

Zhang, X1 Guo, H1, and Chen, C1


1 Key Laboratory of Carbon Materials, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, P. R. China.

2Research Institute of Chemical, Yangquan Coal Industry (Group) CO.,LTD, Taiyuan P. R. China.

Here, graphene used to enhance mechanical properties and radiation performance of infrared radiation coating. By means of the Thermal Infrared Emissivity Instrumet (TIR 100-2), measured the thermal radiation property of graphene infrared radiation coating. The structure and mechanical properties of the film are characterized by use of SEM, TG-DTA, and XRD. The effects and also the relationship between contents and sizes of graphene on the radiation performance and the mechanical properties of infrared radiation coating, such as adhesion, scratch resistance and abrasion resistance were studied experimentally. Result show that the mechanical properties and the radiation performance of coating were improved with high the increase of mass fraction of graphene of it. Optimum infrared radiant characteristics can be obtained in the sample of graphene 0.1 wt%, 0.5 wt%, 0.1-1μm sizes, which exhibits infrared emissivities of 0.89 and 0.91 in the whole band and 0.8～15μm band, respectively, The pencil hardness(3H), adhesion（＞98%) and abrasion

are tested, and shows a predicted result. Thus we pointed out the proper route to improvement in the radiation quality of the infrared radiation paint, providing a theoretical basis for further theoretical study as well as for bringing into full play its role of emit heat in the form of infrared radiation.

306

Graphene-Nanodiamond Hybrid Materials: Microstructure and Hierarchical Defects Evolution with Electron Beam Irradiation

Gupta, S1,*, Heintzman, E1, Jasinski, J2

* [email protected]


Kentucky University, Bowling Green, KY 42101, USA 2 Department of Chemical Engineering and Conn Center for Renewable Energy,

University of Louisville, Louisville, KY 40292, USA

Hybrid nanomaterials are an interesting class of materials that can find applications in diverse fields owing to their multifunctionality tailored at the interface of the constituents. We report the structural and physical properties of novel nanocarbon hybrids of variants of graphene (graphene by itself, graphene oxide; GO and reduced graphene oxide; rGO) and ultradispersed diamond forming truly tetragonal- trigonal nanocomposites ensemble subjected to electron-beam (EB) irradiation from transmission electron microscope electron gun operating at primary acceleration voltage ~200 kV. The structural defects evolution was monitored with time under EB irradiation combined with selected-area electron diffraction. They were also characterized using resonance Raman spectroscopy (RS) and Raman mapping and room temperature electrical property measurements. Experiments showed that irradiation generates microscopic lattice point defects (most likely vacancies) in a hierarchical manner much below amorphization threshold (<15 mins.), beyond which it leads to amorphization as apparent from both the TEM and RS techniques. However, the nanocomposites and especially GO and rGO show radiation resilience by stabilizing defects where nanodiamond behave like defect sink elucidated through the intensity, bandwidth, and band position variation in prominent RS signatures. We gratefully acknowledge financial support from NSF-DMR, NSF KY EPSCoR, NASA KY EPSCoR and WKU Research Foundation RCAP grants.

307

Graphite nanoplatelets coated with polymer and silica nanoparticles for thermally conductive and electrically insulating polymer composites

Kim, Yongse1, Won, Eunju1, Shin, Solbi1, Goak, Jeungchoon1, Lee, Naesung1

Department of Nanotechnology and Advanced Materials, Sejong University, Seoul, Korea

*E-mail address: [email protected]

Polymer nanocomposites have rapidly enlarged their applications in electronics due to their attractive properties easily manipulated by incorporating different kinds and contents of nanomaterial fillers. For instance, heat dissipating capability and light weight are required for heat dissipaters of LEDs, which can be achieved by engaging thermally conductive and lightweight filler materials in polymer composites. Nanocarbon materials such as graphite nanoplatelets (GNPs), graphene, and carbon nanotubes (CNTs) have been used as one of the best candidates for this purpose. Thermal conductivity of composites is improved by increasing the filler content, but over their percolation threshold, the composites may suffer a problem of electrical short. This problem can be solved by modifying nanocarbon materials to be electrically insulating while maintaining their excellent thermal conductivities. Recently, it has been studied that nanocarbon materials have been coated in various ways by electrically insulating layers such as silica using surfactants and sol-gel processes. We also coated GNPs with poly (melamine-co-formaldehyde) methylated (PMF) and silica nanoparticles by a simple process and achieved electrical insulation of GNPs. Epoxy-based composites, highly loaded with PMF- and silica-coated GNPs, demonstrated their excellent thermally conductive but electrically insulating properties.

308

Highly graphitic porous carbons and their metal oxides composites for ORR reaction

Wang, M1, Su, C1, Wang, S.1, Liu, J1


1 Curtin University, Western Australia, Australia

Highly graphitic porous carbon nanoparticles are successfully synthesized via facile fabrication method using cheap, abundant and low toxic metal oxides. Such metal oxides could be easily removed by simple acid washing which gives the almost metal free final carbon products. Moreover, the degree of graphitization can be simply controlled through the adjustment of carbonization temperatures. Oxygen reduction reaction is carried out to test the electrochemical catalytic ability of the graphitic porous carbon nanoparticles, and such sample exhibits relatively good performance at the condition of pure carbon nanoparticles without any nitrogen or phosphorous doping.

309

Study on the heating behaviors of SiC fiber mat under microwave irradiation

Cho, K 1, Khishigbayar, K 1, Kim, K 1


1 Korea Institute of Ceramic Engineering and Technology, Jinju-si, South Korea

SiC fiber mat shows ultra-fast heating under the microwave irradiation. SiC fibers have been reacted different ways with microwave irradiation depending on their fabrication conditions. The optimization of curing and pyrolysis conditions used for fabrication of SiC fiber can play main role for heating efficiency of SiC fiber mat, according to the results of thermal analysis. The influence of these properties on microwave heating effect have been analyzed with electromagnetic field in the stirrer type microwave oven with thermal measurement IR-camera. It confirmed that SiC fibers can be heated by microwave in 2.45GHz of frequency. The highest temperature on the SiC fiber surface is up to 1600 °C and temperature distribution is uniformly appeared on the mat surface. The microstructure of fabricated SiC fibers was changed remarkably by the iodine vapor curing at low pressure. The early stage crystallization of β-SiC avoids oxygen uptake into the fiber, which could lead to increase heating efficiency of SiC fiber under microwave.

310

Heating property of N-doped graphite fibers by urea treatment

Min-Ji Kim, Kyeong Min Lee, Hanjoo Jo and Young-seak Lee *




In this study, nitrogen doped graphite fiber (GFs) have been prepared using urea by thermal solid-state reaction to improve their heating property. The surface properties of N-doped GFs have been examined by XPS. Their electrical resistance and heating properties have been also determined a Programmable electrometer and thermo-graphic camera, respectively. XPS data showed that pyridine, pyrrolic/pyridone, quaternary and oxidized nitrogen were introduced on GFs during the urea treatments. Heating property of the GFs was improved as nitrogen functional groups introduced onto ones. The maximum surface temperature of GF treated was observed 53.8 at 60 V, and the heating property was increased about 55 % compared to non-treated GFs. These results are attributed that introduced nitrogen functional groups on GFs help to improve the electric conductivity of GFs.

311

Hetero Atom Doped Porous Carbon from Asphaltene for Oxygen Reduction

Y Zhou*, YL LI, RF Liu, N Xiao, CL Wang, P Wan, JS Qiu


Carbon Research Laboratory, Liaoning Key Lab for Energy Material and Chemical Engineering, State Key Lab of Fine Chemicals, School of Chemical Engineering, Dalian

University of Technology, Dalian, China

Oxygen reduction reaction (ORR) is a critical process in fuel cells, which is normally catalyzed on cathodes by Pt-based catalysts. The limited natural reserves and high price of Pt, together with the issues of instability and deactivation by CO poisoning and crossover effect, have hindered the large-scale application of fuel cells. Therefore, the development of novel and high efficient ORR catalysts are the key to solving these problems. Nano-carbon materials, because of its unique structure and properties are widely used in catalyst, adsorption, energy conversion and storage, and other fields. Recent work has shown that heteroatom doped nano-carbon materials has an enhanced catalytic activity for ORR. Heavy carbon resources like asphaltene, exhibiting excellent graphitizable property, high carbonization yield and little ash content, are commonly used in carbon industries. In this work, N、S co-doped porous carbons have been synthesized using heavy organic matters of coal as carbon source by a convenient process. The electrochemical test results show that the sample NSAC-700 has better catalytic activity for oxygen reduction reaction, close to the business Pt/C catalyst. The catalytic activity of the samples were improved by the increase of activity sites on the surface of the materials resulting from the synergistic effect of nitrogen and sulfur atoms led to better electro-catalysis performance than the un-doped porous carbon. The initial potential of NSAC-700 is about -0.17V vs Ag/AgCl, the limiting current density is as high as 4.8mA/cm2. The stability tests show that Pt/C about 40% the loss of catalytic activity, and NSAC-700 only 25% the loss of activity after cycles 20000 s. This indicates that NSAC-700 has good methanol tolerance in alkaline environment. ACKNOWLEDGEMENT: This work was supported by National Natural Science Foundation of China under Grant No. 21576047, U1510204, 21276045

312

Heteroatom-Codoped Carbon Nanosheets For High-Performance Lithium-Ion Batteries Anodes

Chen Y , Yuan Q, Shi L, Guo S, Chen X, Ma Z, Zhou J and Song H*

Presenting author’s e-mail: [email protected] * Corresponding author’s e-mail: [email protected]

State Key Laboratory of Chemical Resource Engineering, Beijing Key Laboratory of

Electrochemical Process and Technology for Materials, Beijing University of Chemical Technology, Beijing 100029, P. R. China.

Heteroatom-doped carbon materials have attracted considerable interests as lithium ion batteries (LIBs) anodes. In this work, nitrogen and sulphur co-doped carbon nanosheet (NSCNS) has been prepared by a template method with the assistance of potassium chloride. The obtained NSCNS possesses two-dimensional ultrathin structure with the thickness of ca. 5 nm, and pack with each other. Heteroatoms are confirmed to be present in NSCNS with the atomic percentage of 5 % for nitrogen and 1 % for sulphur. Amounts of defects and localized graphene nanocrystallites coexist in NSCNS, which can provide reaction sites for lithium storage and enhance the electrochemical performance. When evaluated as LIBs anodes, NSCNS exhibits a reversible capacity of 1200 mAh g-1 at 200 mA g-1 after 50 cycles, and maintain 800 mAh g-1 at 1 A g-1 after 200 cycles, indicating a good cyclic stability and superb rate performance. The finding about NSCNS is beneficial for preparing advanced heteroatom-doped carbon electrodes for LIBs.

313

Heteroatoms Doped Magnetic Carbons For the Enhanced Cr(VI) Removal

Yonghai Cao1, Zhanhu Guo2, Hao Yu1 and Feng Peng1


1School of Chemistry and Chemical Engineering, South China University of Technology,

Guangzhou, Guangdong 510640, China 2 Integrated Composites Laboratory (ICL), Department of Chemical and Biomolecular

Engineering, University of Tennessee, Knoxville, TN 37996, USA With the growth in various industries, such as metal cleaning, electroplating, pigment, mining and leather processing, heavy metals (Cr, Cd, Hg, Pd and As) have become a widespread pollutant in the surface water and groundwater. Cr(VI), a typical heavy metal ions, is a commonly identified contaminant because of its high toxicity and mobility. Recently, magnetic carbon nanocomposites with large specific surface area were introduced to remove the heavy metal in the wastewater and displayed the excellent efficiency. In this work, we successfully synthesized the novel heteroatoms (N, F etc.) doped carbon composites with higher magnetism and specific surface areas using melamine or poly (vinylidene fluoride) as carbon and nitrogen/fluorine source through a simple pyrolysis method. After that, we utilized the as-synthesized materials to treat the Cr(VI) solution, and found that the excellent performance were observed (removal capacity based N doped carbon adsorbent: 29.46 mg/g, PH at 7; 2001 mg/g, PH at 1), which can be attributed to the heteroatoms dopant and the iron nanoparticles on the surface. The heteroatoms dopant on the carbon surface can increase its negative charge density and then enhance the ability for the adsorption of Cr(VI) ions. These results demonstrated that heteroatoms doped magnetic carbon nanocomposites are the promising materials for the environmental remediation.

314

Hierarchical porous carbon synthesis from ACM mixture for EDLCs

Chang, PP 1, Wang, CY 1, Chen, MM 1.

[email protected] [email protected] [email protected]

1 Key Laboratory for Green Chemical Technology of MOE, School of Chemical Engineering and Technology, Tianjin University, Tianjin, P. R. China

A series of porous C/C composites were prepared by KOH activation from a mixture of graphite oxide and coal tar pitch-based amphiphilic carbonaceous material (ACM-CP). They were used as electrode materials of electric double layer capacitors (EDLCs). Porous carbon nanoparticles derived from ACM-CP fill in the conductive frame structure made up of few-layer graphene microsheets that were synthesized by exfoliation and the following heat-reduction of graphite oxide. The porosities of these composites mainly come from the filled ACM-CP deriving nanoparticles. Hence, an optimized sample owns, at the same time, ample specific surface area (SSA) of 2562 m2 g-1, high sp2-bonding carbon content of 88.2% and sufficient intrinsic e-conductivity of 120 S/m. Even totally free of conductive agent such as carbon black (CB), the resultant electrode still achieved high gravimetric capacitance at 50 mA/g of 288 F/g with rate capacity C100/0.05 of 60.4% in 6 M KOH electrolyte and of 130.4 F/g with rate capacity C10/0.05 of 56.8% in 1 M TEABF4/PC electrolyte, respectively. Significantly, without any CB, the resultant electrode could run independently up to 10,000 cycles at 10 A/g with capacitance retention of 95.8% in 6 M KOH electrolyte, at 1 A/g with capacitance retention of 78.3% in 1 M TEABF4/PC electrolyte. In summary, the conductive hierarchical porous carbons have promising applications in EDLCs.

315

Hierarchically porous carbon derived from biomass for high performance supercapacitor

Choi, M.S1, Park, H.S1

[email protected]

1 Sungkyunkwan University, Suwon, South Korea

Nowadays, studies on biomass conversion technologies are carrying out intensively. Biomass is expected as a promising material for application in energy storage systems due to their properties such as abundance and ease of processing. Herein, a facile synthesis of hierarchically porous, chemically activated carbon materials derived from biomass is investigated. Empty fruit bunch (EFB) was used as the carbon source due to the abundance, low cost, sustainability and high lignin-content. The carbon substances in EFB including lignin-based materials were condensed and carbonized into the bulk solid via a hydrothermal carbonization (HTC) process. After chemical activation process using KOH, the carbon materials were transformed into the hierarchical porous structure consisting of macro- and micropores. As confirmed by various characterization results, the optimum activation temperature for supercapacitor application is determined as 700 C. Finally, the as-optimized sample which is named as KOH-activated porous carbon in 700 ˚C (KAPC700) exhibited outstanding capacitive performance with a specific capacitance of 402.3 F g-1 at 0.5 A g-1, superior rate capability of 79.8 % at current densities from 0.5 A g-1 to 10 A g-1, and remarkable life cycle behavior of 10000 cycles with 96.5 % capacitance retention at 20 A g-

1. On the basis of their ultrahigh specific surface area of 2861.4 m2 g-1 based on hierarchical porosity and low electrical resistance of the electrode, the exceptional ion and electron transport properties of this porous carbon are observed to be an asset for high power supercapacitor.

316

High Capacitance at High Scan Rate by Hybrid Graphene-Carbon Xerogel

Supercapacitors

Ramos-Fernández G.1, Canal-Rodríguez M.2, Arenillas A.2, Menéndez J.A. 2, Martin-Gullón I.1

[email protected]

1University of Alicante, Alicante, Spain 2INCAR-CSIC, Oviedo, Spain

We report the preparation and characterization of a graphene doped-carbon xerogel supercapacitors by a simple modification of the traditional sol-gel polymerization of resorcinol-formaldehyde mixtures, carried out in the presence of an aqueous suspension of graphene oxide, in order to grow the gel from imbibed graphene oxide sheets. Organic hybrid xerogels were prepared at four graphene oxide loadings. These xerogels were further carbonized in nitrogen atmosphere at 800ºC attaining medium pore developments (700-800 m2/g BET), where graphene oxide is in situ reduced increasing the electrical conductivity. Subsequently, portions of these hybrid graphene-carbon xerogels were steam activated at two burn-offs to increase microporosity for the improvement of the electrochemical properties, combining by the double effect of conductivity plus porosity. The addition of graphene oxide to the resulting electrodes yielded an increase of electrical conductivity up to 3 times for the hybrid non-activated carbon xerogels, with stable capacitance values of 150 F/g at high scan/sweep rates, and an increase of 167% in power density with respect to the undoped non-activated xerogels. Contrarily to it was expected, steam activated samples with high pore developments (above 1500 m2/g) but not so high conductivity, did not improve the electrochemical performance, which means that the conductivity plays a more relevant role than medium-high pore development. These results might suppose a milestone in carbon xerogel products, since a better results are got with a higher yield product (i.e. just carbonized), and consequently with a cost-effective economic process.

317

High charge-discharge rate properties of graphite foams for lithium-ion batteries

Sangmin Lee, Ji-Hyun Kim, Do Young Kim, Min-Jung Jung, and Young-Seak Lee*




Graphite foams (GFms) are fabricated with hydrogel template method using mesophase pitch (MP) and polyvinylalcohol-acrylic acid (PVA-AAc) solution as anode materials for lithium-ion batteries (LIBs). The GFms’ crystalline structure, porosity and electrochemical properties are analyzed by X-ray diffraction (XRD), porosimeter and BLCT battery cycler, respectively. The GFm particles have the developed-crystalline structure (interlayer spacing(d002) of 0.3375 nm and crystalline thickness(Lc) of 29.112 nm) and the porosity of 56.55%. The discharge capacity of fully charged GFm particles electrode indicates 345.3 mAh/g at 30C-rate, within 2 min. This has coulombic efficiency of 92% compared to the discharge capacity at 0.2C. These porous particles fabricated from GFm may be an effective materials to improve the lithium diffusion rate for lithium ion batteries, because a number of pores, channels and slightly higher interlayer spacing of these GFm particles reduced diffusion distance and increased pathways of lithium ions.

318

High Performance Anodic Graphite for Li-Ion Batteries Using Hyper Coal

Chung D1, Nakabayashi K1,2, Miyawaki J1,2, Yoon SH1,2


1 Interdisciplinary Graduate School of Engineering, Kyushu University, Fukuoka, 816-8580, Japan

2 Institute for Materials Chemistry and Engineering, Kyushu University, Fukuoka, 816-8580, Japan

Li-ion battery (LIB) attracts much attention as a reliable power supply for electric vehicles and large energy storage system. To meet the large-scaled requirement of anodic graphite, it is strongly required to develop it using the cheap resource for lowering the production cost of anodic graphite. Hyper coal (HPC), which is a kind of direct solvent-extracted coals, is now expecting as one of the most promising candidates for the precursor of anodic graphite due to the very little ash contents because HPC is produced through a filtration of direct solvent-extracted coal at 350-430oC under high pressure. However, the production of graphite from HPC usually suffers enormous percolation in the conversion process from HPC to coke, and this induces poor electrochemical performance for anode of LIBs. In this study, we examined the effectiveness of natural graphite (NG) as an inhibitor for the percolation in coking. The various ratios of HPC/NG were used for the preparation of cokes, and their derived graphites. Physical and electrochemical properties of the prepared anodic graphites were closely examined.

319

High Performance Digital X-Ray Tube Fabricated Using Carbon Nanotube Emitter

Kang, J -T1, Jeong, J -W1, Choi, Y C1, Park, S1, Kim, J -W1, Jeon, H1,2, Go, E1,2, Lee, J -W1,2, Kim, S1, Yeon, J -H1, Song, Y -H1,2


1Electronics and Telecommunications Research Institute, Daejeon, Republic of Korea 2University of Science and Technology, Daejeon, Republic of Korea

Carbon nanotube (CNT) field emitters have been considered to be one of the best electron sources because of their high emission capability with an easy fabrication process. Specifically, a cold-cathode x-ray tube using the CNT field emitters is expected to overcome the limitations of conventional thermionic x-ray tubes, such as analog operation and slow response time. The CNT x-ray tube can be digitally addressed with a fast response time, which makes it possible to give a very short exposure time. The high x-ray dose rate at a very short exposure time is critical for achieving high resolution x-ray images. In the present study, we have developed high-performance CNT field emitters with good reliability, uniformity, and reproducibility. Furthermore, we successfully fabricated a digital x-ray tube with the CNT emitters showing high-speed, high rate operation needed for medical applications.

320

Highly porous, activated carbon nanotubes as electrode/separator for lithium-sulfur batteries

Jian-Qiu Huang1, Jang-Kyo Kim1


1Department of Mechanical and Aerospace Engineering, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong

Kong, PR China

Highly porous and conductive carbon nanotubes (aCNTs) are synthesized by activation using potassium hydroxide. The aCNTs are employed as both hosts for sulfur incorporation and barrier layers for preventing polysulfide diffusing to the anode. For the latter, aCNTs are coated directly on the pristine separator. The amount of aCNTs on each part is systematically varied to investigate their influence on the capability and cyclic stability of lithium-sulfur batteries. The battery with an optimal design consisting of an aCNT/S composite electrode and an aCNT modified separator presents an excellent reversible capacity of 621 mAh/g after 500 cycles with a low capacity decay of 0.043% per cycle at 0.5 C (1 C=1675 mA/g). The encouraging electrochemical performance arises from the synergistic characteristics: namely, (i) the porous and conductive aCNT network facilitates fast electron/ion transport and easy electrolyte penetration in the electrode, allowing full utilization of active materials; and (ii) the aCNT layer applied on the separator effectively constraints polysulfide shuttling by immobilization of polysulfides via strong adsorption onto the micropores of aCNTs.

321

High-temperature oxidation behaviour of plasma-sprayed ZrO2 modified La-Mo-Si composite coatings

Wang, C.C.1, Li, K.Z.1, Shi, X.H.1, He, Q.C.1, Huo, C.X.1,

Author’s e-mail: [email protected], [email protected], [email protected], [email protected], [email protected];


Plasma-sprayed ZrO2-modified LaB6-MoSi2 coating (ZLM) was firstly fabricated onto SiC-coated carbon/carbon (C/C) composites to obtain an improved oxidation resistance at 1773 K involving long-term oxidation and short-term cyclic oxidation in an atmospheric environment. LM coating, i.e. the un-doped LaB6-MoSi2 coating, was also fabricated for comparison. The as-prepared ZLM coating possessed somewhat smoother surface. Mass loss of the specimen coated with ZLM coating was only 0.61 % after 30 thermal cycles, which exhibited better than LM coating (2.54 %). After exposure at 1773 K for 140 h, the mass loss percentage of the ZLM coated specimen (0.96 %) was nearly three times lower than that LM coating (3.25 %). The formation of through-thickness-cracks and horizontal cracks within the LM coating resulted in earlier failure for it. Whereas, superior integrated structure of the ZLM coating provided by the continuous Zr-La-Si-O protective scale gave rise to the remarkable oxidation resistance of ZLM coating.

322

High-temperature oxidation behaviour of plasma-sprayed ZrO2 modified La-Mo-Si composite coatings

Wang, C.C.1, Li, K.Z.1, Shi, X.H.1, He, Q.C.1, Huo, C.X.1,

Author’s e-mail: [email protected], [email protected], [email protected], [email protected], [email protected];


Plasma-sprayed ZrO2-modified LaB6-MoSi2 coating (ZLM) was firstly fabricated onto SiC-coated carbon/carbon (C/C) composites to obtain an improved oxidation resistance at 1773 K involving long-term oxidation and short-term cyclic oxidation in an atmospheric environment. LM coating, i.e. the un-doped LaB6-MoSi2 coating, was also fabricated for comparison. The as-prepared ZLM coating possessed somewhat smoother surface. Mass loss of the ZLM coating was only 0.52 % after 30 thermal cycles, which exhibit better protective capability for C/C composites than LM coating (2.54 %). Simultaneously, after exposure at 1773K in air for 100 h, the mass loss percentage of ZLM coating (2.15 %) was nearly six times lower than that LM coating (12.16 %). The presence of through-thickness-cracks and horizontal cracks within the LM coating led to earlier failure for it. Whereas, superior integrated structure of the ZLM coating provided by the continuous Zr-La-Si-O protective scale gave rise to the remarkable oxidation resistance of ZLM coating.

323

High-voltage aqueous supercapacitors based on solvated graphene films

Liu, CC1, YANG, XW1, Yan, XJ1

Presenting author’s e-mail: Liu, CC [email protected] Yang, XW [email protected] 1 School of Materials Science and Engineering, Tongji University, Shanghai 201804, P. R. China Electrochemical capacitors, known as supercapacitors, have drawn a worldwide attention because of their high power densities, long cycle lifetime, and fast charging capabilities. Nowadays, activated carbon (AC) is the most conventional electrode materials for supercapacitors due to their high specific surface area. The energy density of supercapacitors is proportional to the capacitance and the square of voltage. Therefore, extensive research aims at increasing the operating voltage of supercapacitors. In aqueous electrolytes, the working voltage is usually less than 1.0 V, whereas it is in the range of 2.5 - 2.7 V for organic electrolytes. Unfortunately, the latter presents serious disadvantages, such as insecurity, low conductivity and moisture isolated building atmosphere, and they are environmentally unfriendly. Thus, aqueous supercapacitors seem to be more acceptable from an aspect of practical application in the long term. This study reports a high-voltage symmetric supercapacitors based on solvated graphene electrode in highly concentrate aqueous lithium salts electrolyte. Compared with the traditional AC electrode, the maximum potential of the solvated graphene films remain stable during operation of the supercapacitors at 2.5 V in this aqueous electrolyte. The solvated graphene films exhibited gravimetric capacitance of 156 F g-1 at a current density of 0.2 A g-1, and retained 105 F g-1 when the current density was increased up to 10 A g-1. This high-voltage aqueous supercapacitors revealed good cycle stability retaining nearly 90% of the initial capacitance after 5000 charge/discharge cycles.

324

Surface Characteristics of Nitric Acid Modified Activated Carbon and the Catalytic Performance for Methane Reforming of Carbon Dioxide

Zhang, G1, 3, Liu, J1, Su, A1, Xu, Y1, Zhang, L1, Li, H2, Zhang, J1, Zhang, Y1

Presenting author’s e-mail: [email protected]; [email protected]

1 State Key Laboratory Breeding Base of Coal Science and Technology Co-founded by Shanxi Province and the Ministry of Science and Technology, Taiyuan University of

Technology, Taiyuan, Sahnxi, China 2 Shanxi Lu’an Mining Group Co., Ltd, Changzhi, Shanxi, China

3 State Key Laboratory of Coal and CBM Co-Mining, Jincheng, Shanxi, China

Coal based activated carbon was modified by nitric acid under various preparation conditions. The surface structures of activated carbons were observed and analyzed by SEM and BET methods. Boehm's titration and XPS methods were applied to analysis the functional groups and elements on the carbon surface. The catalytic performance for methane reforming of carbon dioxide was investigated. The results showed that the activated carbon prepared by nitric acid modification had good catalytic properties. Through single-factor analysis, the optimization of the modified parameters were obtained, at a calcination temperature of 800 , a calcination time of 80 min, a HNO3 concentration of wt. 8% and a calcination time of 80min. Results of characterization analysis showed that graphitization degree, surface area and pore volume of activated carbon increased and surface C-O, O-H and alkyl C-H groups decreased after nitric acid modification, with no obvious change in pore size. It also found that the ionic OH-, pyridine, pyrrole and amino nitrogen functional groups were generated. Under the optimal modified conditions, 10.8% CH4 and 16.2% CO2 conversion can be improved, 28.3% CO and 5.2% H2 yield can be improved over modified activated carbon, respectively. Enlargement of surface area and pore volume, generation of the ionic OH-, pyridine, pyrrole and amino nitrogen functional groups will benefit to enhance the reforming conversion of methane and carbon dioxide. On the basis of experimental observations characterization analysis and literature, a simple carbon dioxide reforming of methane into syngas mechanism over an activated carbon catalyst modified by nitric acid is proposed.

325

Hot spraying graphene coating for corrosion inhibition Zhang R1,2. Li Y1, Li Z2., Chen D1.

1Chemical Engineering Department, Norwegian University of Science and Technology, Sem Sælands vei 4, 7491 Trondheim, Norway

2College of Pipeline and Civil Engineering, China University of Petroleum (East China), Qingdao 266000, China


Great efforts are underway to develop materials for inhibit metal corrosion, which costs industries significantly. Here we introduce a hot spray coating technique to produce graphene protection layers on copper to prevent corrosion, where the graphene were produced by simple, low cost and environmental friendly electrochemical exfoliation method. However, as coated graphene layer accelerated corrosion. After mild thermal treatment of the coated layer, a dense graphene protection layer is formed on the Cu surface. The resulted protect layer exhibited very good anti-corrosion properties for copper in NaCl media. Further investigation revealed that the anti-corrosion ability of graphene layers is highly affected by thermal treatment temperature and the surface density of graphene. The optimum sample has a surface density of 0.53 mg·cm-2 and was thermal treated under 400 °C (G/Cu-400). The corrosion rate of G/Cu-400 is as low as 0.04 mm/year, 6 times lower than it of bare copper. The total corrosion resistance is 2812 Ω·cm2, and the corrosion inhibition efficiency is as high as 83.3 %. These results showed that the uniform graphene coating produced by our technique is capable of covering the copper surface properly and inhibiting corrosion in harsh environments when the surface density and temperature of heat treatment is appropriate.

326

Hydrogen transfer phenomenon on carbon materials with different edge structures

Umeda, D, Togo, T, Yasuhiro, Y, Satoshi, S


Chiba University, Chiba, Japan

Chemisorption of hydrogen on carbon materials is expected to be applied to hydrogen storage, but the detailed mechanism of hydrogen transfer phenomenon has not been clarified. In this study, we aimed to elucidate the hydrogen transfer phenomenon on the edge of carbon materials by analyzing hydrogenation and dehydrogenation of various aromatic compounds. 9,10-Dihydroanthracene (DHA), 9,10-dihydrophenanthrene (DHP) and adamantane were sealed in a glass ampoule tube under reduced pressure and heated at 573-803 K to examine dehydrogenation temperature from sp3C-H to sp2C-H. In addition, hydrogenation experiment of tetracene was conducted by heating hydrogenated aromatic compounds at 473-673 K under a hydrogen pressure of 0.9 MPa. These samples were analyzed using elemental analysis and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Transition states of dehydrogenation and hydrogenation were calculated using DFT calculation (Gaussian 09, b3lyp/6-31 g (d)). Decrease in the number of hydrogen of DHA was confirmed by elemental analysis at 723 K or higher, and sp3C-H peak disappeared at that temperature as results of DRIFT analysis. From these results, it was estimated that dehydrogenation of DHA proceeded at 723 K. Such dehydrogenation proceeded at 773 K for DHP and 783 K for adamantane. We found that the zigzag type structure tends to be dehydrogenated the most, since sp3C-H of DHA was the easiest to be dehydrogenated. Hydrogenation of tetracene proceeded at positions 5 and 12 at 773 K. From these results, it is concluded that the tetracene-like structure is most effective for adsorption and desorption of hydrogen.

327

Hydrothermal carbonization with Ammonium Salts for Producing Nitrogen Doped Carbon

Kenneth G. Latham1, Michela I. Simone, Wesley M. Dose2, Jessica A. Allen1, Scott W.

Donne1


1 University of Newcastle, Newcastle, Australia 2Argonne National Laboratory, Argonne, Illinois, USA

The doping of carbon materials with nitrogen has been investigated using several approaches, such as electric arc, pyrolysis, hydrothermal and pre- or post-treatments with nitrogen sources. At present, hydrothermal carbonization offers one of the most environmentally friendly approach to the formation of functionalized nitrogen doped carbon structures. This is due to carbonization occurring under water at substantially lower temperatures (180°-300°C) in closed systems where almost no gases are produced. Furthermore, surface functionality, chemical structure and morphology is easily controlled through the modification of reaction conditions (i.e., temperature, residence time, pH). Finally, the incorporation of nitrogen into the structure can be achieved by adding soluble nitrogen containing compounds into the hydrothermal solution prior to carbonization. In this study, we have investigated the effects of different ammonium containing anions ((NH4)2SO4, (NH4)2HPO4, NH4Cl, (NH4)2Fe(SO4)2) on the surface composition of hydrothermally produced carbons to easily modify nitrogen functionality. This was examined via Near Edge Adsorption X-ray Fine Structure (NEXAFS) and X-ray Photoelectron Spectroscopy. Additionally, these carbons were also tested electrochemically and found to displayed a wide range of capacitances from 70 F g-1 to 275 F g-1 in 5 M KOH, exhibiting pseudocapacitance as well as electrical double layer capacitance.

329

Impact of fullerene-like structures in carbon materials

Jacob Martin1*, Radomir Slavchov1, Edward Yapp2, Jethro Akroyd1, Sebastian Mosbach1 Markus Kraft1,2

[email protected]

1 Department of Chemical Engineering and Biotechnology, University of Cambridge 2 School of Chemical and Biomedical Engineering, Nanyang Technological University

What has previously been considered disordered carbon in soot,1 activated carbon2 and glassy carbon3 is now being considered to be curved fullerene-like structures. Curvature is integrated into sp2 carbon structures through the enclosure of a pentagon within a hexagonal lattice, which creates a point defect and significant strain on the lattice. This strain polarises the π-bonding network leading to a significant dipole moment of 2.07 Debye for the simplest case (corannulene), which is on the order of water (1.85 Debye). In this work, we make use of electronic structure methods to study the size of the dipole moment for a range of different curved aromatic molecules found in non-graphitising carbons. We then explore the origin of the dipole moment and construct a geometric model for describing the dipole moment in any condensed aromatic molecule. We also develop a distributed multipole description of the electrostatics allowing for integration of the effects of π-polarisation for use in forcefields. Finally, we comment on the impact on the interaction of ions and molecules with these curved aromatic molecules in soot and activated carbon.

Figure 1 – Electrostatic potential around coronene a flat polycyclic aromatic hydrocarbon a) and corannulene a curved

polycyclic aromatic hydrocarbon b,c) at the van der waals surface (iso=0.001 eÅ-3). Cross section of electrostatic potential showing the polarised negative potential (red) which leads to a strong dipole moment. [1] E. Yapp et al. (2017). Modelling PAH curvature in laminar premixed flames using a detailed population balance model. Combustion and Flame, 176, pp. 172-180. [2] Harris, P. J. F., Liu, Z., & Suenaga, K. (2008). Imaging the atomic structure of activated Carbon, 20, 1–5. [3] Harris, P. J. F. (2004). Fullerene-related structure of commercial glassy carbons. Philosophical Magazine, 84(29), 3159–3167.

330

Improved Amine Functionalisation of Few-Layer Graphenes and Non-Aqueous Titration Analysis

Smith, E A M 1 2, Crean, C 1, Slade, R 1, Spacie, C 2, Stirling, C 2, Watson, D 1

[email protected]

1 University of Surrey, Guildford, Surrey UK 2 Haydale Ltd, Ammanford, Carmarthenshire UK

Three differing ammonia plasma treatments were applied to few-layer graphenes using Haydale Ltd’s HDPlas® process and produced materials with varying levels of nitrogen (atomic%). The materials were characterised with X-ray photoelectron spectroscopy, acid-base titration and zeta potential determination. Acid-base titration showed that these amine-functionalised materials have similar levels of reduced acidity when compared to the starting material. The surface charge, as measured by zeta potential determination, differentiates the level of treatment. A non-aqueous titration method has been applied to quantitatively determine the extent of amine functionalisation.

331

Improved toughness of carbon fiber/epoxy composites with in-situ toughening agents

Jeong, E1, Bae, J-S1, Kim, T1, Lee, J2, Woo, H1


1 Kyungpook National University, Daegu, Republic of Korea 2Yeungnam University, Gyeongbuk, Republic of Korea

Carbon fiber/epoxy composites have been researched due to their excellent mechanical properties such as specific strength and modulus. Although these excellent mechanical properties seems to enable their uses as structural materials for automotive and aerospace applications, the applications of carbon fiber/epoxy composites are still limited due to their poor fracture toughness and impact strength, arisen from the inherent brittleness of the epoxy matrix resin. Polysulfone based polymers are one of the best toughening agents to overcome the brittleness of epoxy resin, resulting in improved toughness and impact strength without lowering Tg of the composites. However, the use of these toughening agents significantly increases the viscosity of epoxy matrix resin. Hence, the polysulfone based toughening agents cannot be used for carbon fiber/epoxy composites prepared by resin transfer molding(RTM) or vacuum infusion molding(VIM), which is very useful to prepare composite parts with complicated shapes. This study aims to develop a new toughening agent, which can be used with RTM or VIM process without increasing the viscosity of epoxy matrix and decreasing Tg of the composites. The new toughening agent are prepared using azide-alkyne click chemistry and used for carbon fiber/epoxy composites prepared with VIM process. The toughness and impact strength of resulting composites are evaluated with flexural tests and drop weight tests.

332

Improvement of De-NO2 performance of activated carbon fibers by deposition of potassium species

Ryu DY1, Shimohara T2, Nakabayashi K1,2, Miyawaki J1,2, Yoon SH1, 2.*




The effectiveness of phosphorus, potassium, and the other mineral compounds, which were supported on the surface of cellulosed based activated carbon fiber, on the removal of NO2 was already reported. In this study, we comparatively examined the effects of impregnation of K and P

compounds, for example, mono-potassium phosphate (KH2PO4), potassium acetate (CH3COOK), and phosphoric acid (H3PO4), which were impregnated on the surface of the pitch-based ACF, on the removal of NO2 at atmospheric conditions. As a result, the 2 M of CH3COOK-loaded pitch-based ACF showed 2.8 times longer breakthrough time than the pristine one, indicating that the deposited potassium species can improve the De-NO2 performance.

333

In Vitro Enterosorption Studies of Indole And P-Cresol Elimination Rate by Rice Husk-Derived ACS

In Vitro Enterosorption Studies of Uraemic Toxins Removal by Biocarbons

Jandosov J1,3, Howell C2, Chenchik D3, Baimenov A3, Kosher B1,3, Ray S2, Mansurov Z1,3, Mikhalovsky S2


1 Al-Farabi Kazakh National University, Almaty, Kazakhstan 2University of Brighton, School of Pharmacy and Biomolecular Sciences, UK

3 Institute of Combustion Problems, Almaty, Kazakhstan Rice husk (RH) is a unique material as a siliceous carbon precursor since it is a large scale renewable bioavailable green material of low commercial value. Three different samples of highly porous carbon enterosorbents were prepared in this study from RH, characterized by physico-chemical methods and investigated for in vitro adsorption studies of uraemic toxins precursors, e.g.: pcresol, indole and indolylacetic acid. The sample CRH475КОН850N was prepared from carbonised RH (CRH) via KOH activation at 850 ºC followed by ammoxidation; the sample CRH475K2CO3950N was obtained from CRH via K2CO3 activation at 950 followed by nitric acid oxidation, urea impregnation and annealing in inert atmosphere in order to functionalise these carbons surface with amino groups. The sample CRHP450 with surface functional phosphate groups was obtained from RH via H3PO4 activation at 450 ºC for 1h at the RH/H3PO4 (w/w) impregnation ratio of 1:2, followed by alkaline solution treatment to remove silica template and excess of phosphates. According to calculations based on QSDFT equilibrium model, surface area and pore volume for CRH475КОН850N reached values of 2330 m2/g and 1.83 cm3/g, and for CRH475K2CO3950N: 1356 m2/g and 0.85 cm3/g, while for CRHP450: 1400 m2/g and 1.56 cm3/g, respectively. The adsorption profile for these toxins precursors revealed that each of the carbons was able to remove clinically relevant levels of the three uraemic toxins from simulated colonic fluid.

334

Interconnected Fe-Mn fibrils on activated carbon to increase As(V) uptake Rangel-Mendez, R1, Gutierrez-Martinez, J1


1 Instituto Potosino de Investigación Científica y Tecnológica, San Luis Potosí, México

The incorporation of La (III), Ce(IV), and Zr(IV), as well as MnO2, into the reticular structure of iron(III) (oxy)hydroxides has been studied, in order to increase the density of hydroxyl groups and thus the selectivity towards As(V). This can be attributed to the distortion of the crystal lattice of iron by introducing an atom of a metal such as those mentioned above. Our contribution is the modification of activated carbon with (oxy)bimetallic hydroxides of Fe-Mn by means of a microwave-assisted hydrothermal synthesis to improve the As(V) removal from water. This hybrid adsorbent material was characterized by Fourier Transform Infrared Spectroscopy (FTIR), X-ray diffraction (XRD), and Scanning Electron Microscopy (SEM). In addition, this material was evaluated in batch adsorption experiments. The results obtained indicate an increase in the maximum adsorption capacity of As (V) from 3.85 mg/g, when we only have Fe, to 6.2 mg/g (at 1.5 ppm and pH 7) with bimetallic hydroxides of Fe-Mn, which demonstrates the synergy of these two (oxy)hydroxides materials. The high adsorption capacity can be attributed to the high density of hydroxyl surface groups, which favors the exchange of ligands between the arsenate ion and the adsorption sites.

335

Investigating Effects of Strontium Bombardment on Glassy Carbon

Odutemowo O.S. 1, Malherbe J.B 1, Njoroge E.G 1, Theron C.C. 1, Wendler E 2. 1 Department of Physics, University of Pretoria, Pretoria, 0002, South Africa

2 Institut für Festkörperphysik, Friedrich-Schiller-Universität Jena, 07743 Jena, Germany


Effects of strontium bombardment and heat treatment on glassy carbon are reported. The modification of the glassy carbon structure due to ion bombardment and annealing was investigated using multi-wavelength Raman Spectroscopy. Three wavelengths for the excitation beam were used namely 244, 514, and 785 nm. The Raman spectrum with the 244 nm wavelength showed the G peak position at 1588 cm-1 which was accompanied with a small D peak. The bombardment of 200 Kev strontium ions resulted in amorphisation of the implanted region with the D and G peak merging into a single broad band. The G peak position reduced from 1588 cm-1 to 1543 cm-1. Atomic force microscopy (AFM) and Scanning electron microscopy (SEM) analysis showed that the surface roughness of the glassy carbon increased from 0.37 nm to 2.29 nm after Sr bombardment. The increase in the surface roughness after implantation was attributed to the enhanced sputtering rate around the polishing marks and other defects where the surface binding energies of the surface atoms were less. The SEM measurement taken for a sample with both implanted and un-implanted edges show that high temperature annealing does not in any way affect the surface of the un-irradiated glassy carbon. High resolution transmission electron microscopy (HRTEM) analysis carried out on the virgin and Sr implanted sample showed that the amorphisation of the glassy carbon structure as a result of ion bombardment was not a complete one. There was still some graphite fringes present in the surface of the glassy carbon.

336

Kinetic Analysis of The Decomposition of Hydroxylammonium Nitrate (Han)-Based Green Propellant With Carbonized Rice Husk (Crh Koh – 700)

Atamanov, M1,3, Smagulova, G1,3, Prikhodko, N1, Hori, K 2, Amrousse, R2, Jandosov, J1,3, Aliyev, E1,3, Mansurov, Z1,3


1 Institute of Combustion Problems, Almaty, Kazakhstan 2Japan Aerospace Exploration Agency(JAXA),3-1-1Yoshinodai,Chuo-

Ku,Sagamihara,Kanagawa252-5210,Japan 3 Al-Farabi Kazakh National University, Almaty, Kazakhstan

In this paper investigated the thermal decomposition of Hydroxylamine nitrate (HAN) and Activated carbon (CRH) with a high specific surface area by EI Mass spectrometry and DTA-TG analysis. The used activated carbon brand CRH-KOH-700 prepared from a carbonized rice husk with a specific surface around 2900 m2/g. Shown the results of the thermal decomposition by electron ionization mass spectrometer at different heating rates (from 16 K/min to 128 K/ min). The study was conducted at a heating temperature of system ranging from 297 K to 723 K under nitrogen atmosphere at a flow rate around 100 ml/min in aluminium pans. The obtained results of the main gaseous products of decomposition of HAN with the addition of activated carbon CRH-KOH-700 at a ratio of HAN – 99% and CRH - 1%. Given the results of a comparison of the intensity of the formation of NO, NO2 and H2O (gas) at the thermal decomposition of hydroxylamine nitrate with carbon additives proposed a possible pathway of reaction of combined decomposition of hydroxylamine nitrate and activated carbon. Also, presented the thermal analysis of decomposition kinetics of investigated above materials by DTA – TG at different heating rates.

337

Shear Alignment of Nematic Phase Graphene Oxide: A mass-producible technique for fabricating large-area graphene-based membranes with nanofiltration properties

Abozar Akbari and Mainak Majumder.


Department of Mechanical and Aerospace Engineering, Nanoscale Science and

Engineering Laboratory (NSEL), Monash University, Clayton, Victoria 3800,.

Graphene-based membranes demonstrating ultra-fast water transport, precise molecular sieving of gas and solvated molecules, have been considered for a host of applications in desalination, gas separation and pervaporation; however scale-up of these membranes to large-areas remains an unresolved problem. Here we are going to present that the discotic nematic phase of graphene oxide (GO) can be shear aligned to form highly ordered, continuous, thin films of multi-layered GO on a support membrane by an industrially-adaptable method to produce large-area in less than 5 seconds1. The pseudoplastic, shear thinning fluid of the nematic phase of GO promotes membrane formation by enhancing wetting and spreading at high shear rates, while resisting dewetting at low shear rates. Pressure driven transport data demonstrate high retention (> 90%) for charged and uncharged organic probe molecules with a hydrated radius above 5 Å as well as modest (30-40%) retention of monovalent and divalent salts. The highly ordered graphene sheets in the membrane plane make organized channels and enhance the permeability of the membrane (71 ± 5 l m-2 hr-1bar-1 for 150 ±15 nm thick membranes). Benchmarking experiments with a highly established commercial nanofiltration membrane demonstrate around 9 times higher water flux at comparable retention values and excellent flux recovery by chemical cleaning. 1. Akbari A, Sheath P, Martin ST, Shinde DB, Shaibani M, Banerjee PC, et al. Large-

area graphene-based nanofiltration membranes by shear alignment of discotic nematic liquid crystals of graphene oxide. Nat Commun 2016, 7.

338

Lignin-derived activated carbon under various KOH concentrations

Hwang, H.1, Choi, J.W.2

[email protected]

1 Department of Forest Sciences, Seoul National University, Seoul, South Korea 2 Graduate School of International Agricultural Technology, Seoul National University,

Pyeongchang, South Korea

For the valorization of residual lignin obtained from pulp and biomass-based biofuel industries to functional materials, high-surface area activated carbon was prepared using lignin as a precursor under different KOH ratios (0, 1:1, 2:1, 4:1, and 6:1, KOH:lignin, w/w). Asian lignin and Inbicon lignin were used in this study. Characterization of each carbon product was also carried out in terms of textural, surface morphological, and structural properties. Before activation process, derivative thermogravimetric analysis was conducted with varying KOH ratios to lignin. As a result, significant changes in thermal stability of lignin were observed that decomposition temperature ranges lowered from 300-400°C for lignin without catalyst to 150-280°C for lignin with catalyst. After catalytic activation process of lignin at 750°C under N2 flow condition with different ratios of KOH, the carbon product with the highest carbon content (85.1%), specific surface area (2644.5 m2/g), and pore volume (1.74 cm3/g) was obtained when the addition ratio was 4. It was superior to commercial activated carbon. Meanwhile, different pore size distribution can be created by controlling KOH ratio and the highest volume of micropores was obtained at the ratio of 2. In order to structural characterization of carbon products, Raman spectroscopy was carried out and Raman spectra was deconvoluted to five Gaussian bands. As the KOH ratio increased up to 4, D/G ratio increased while D/(GR+VR+VL) decreased. This indicates that collapse and rearrangement of the structure occurred followed by incomplete polymerization by catalyst, leading to small aromatic ring formation in carbon products.

339

Low-Cost Carbon Adsorbents for The Removal of Toxic Gases

Velasco, LF1, Berezovska, I1,2, Kerimkulova, AR3,4, Azat, S3,4, Mansurov, ZA3,4, Lodewyckx, P1

[email protected]


2 Macromolecular Materials Laboratory, Department of Materials Science and Engineering, Technion – Israel Institute of Technology, Haifa 32000, Israel

3 Institute of Combustion Problems, 172 Bogenbay batyr Str, 050012 Almaty, Kazakhstan

4 Al-Farabi Kazakh National University, 71 Al-Farabi Ave., 050040 Almaty, Kazakhstan

Emissions of organic vapour pollutants, arising mainly from anthropogenic sources, have an important health and environmental impact. For this reason, and also in order to comply with the increasingly stringent legislation in this matter, it is necessary to further develop materials that can protect more effectively against these hazardous agents. On the other hand, the growing industrial activities have been also accompanied by waste biomass disposal problems. Thus, in this context, the valorization of this kind of residues, which are currently incinerated or go to landfill, into carbon adsorbents is a particularly attractive approach. To attain this goal, low-cost porous carbon materials were obtained from waste biomass precursors (rice husk, apricot stone, Greek walnut) by different activation methods. They were subsequently characterized and tested against the retention of several organic compounds in air streams. Moreover, their shape, textural properties and surface chemistry were tailored to meet the specific needs of the herein studied application. In order to evaluate their adsorption performance, commercial activated carbons largely used in gas filters were also tested as reference materials. The capacity and kinetic results obtained from the breakthrough experiments revealed that some of the synthesized materials are promising adsorbent candidates not only for the retention of single organic compounds but also for mixtures.

340

Low-energy preparation process of TiO2-doped ACFs as CDI electrode materials

Da-Hee Kang, Hanjoo Jo and Young-Seak Lee* Department of Chemical Engineering and Applied Chemistry,


TiO2 doped activated carbon fibers are prepared via low energy process without heat-treatment as capacitive deionization (CDI) electrode materials. ACFs are mixed with different concentration of titanium isopropoxide (TTIP) and isopropyl alcohol solutions. These treated ACFs are dried and then sintered by ultrasonication at room temperature. The morphology and crystallinity of prepared samples are observed by scanning electron microscope (SEM) and x-ray diffraction (XRD), respectively. Contact angles of the electrodes are also measured from water drop on the electrodes to estimate hydrophilic property of the ones. The specific capacitance and desalination performance of TiO2 doped activated carbon fibers are estimated by cyclic voltammetry (CV) and CDI experiments, respectively. The contact angles of prepared electrodes are decreased according to increase TTIP concentrations. On CDI experiments, salt adsorption capacity and charge efficiency of the electrodes are increased from 4.61 mg/g and 0.25 to 7.74 mg/g and 0.58 compared to those of untreated electrodes. These results are attributed that TiO2 doped on ACF surface enhances the wettability of electrode and increases ion-transport rate within ACF pores.

341

Low-temperature synthesis of carbon nanotubes on nickel nanopowders

Medyanova, B1,2, Mansurov, B1, Partizan, G1,2, Jiang, X3, Lesbayev, B1,2


1 Center of Innovation Technologies at the Institute of Combustion Problems, 050050,

Polezhaeva 20, Almaty, Kazakhstan 2 Al-Farabi Kazakh National University, 050040, al-Farabi ave., 71, Аlmaty,

Kazakhstan 3 Institute of Materials Engineering, University of Siegen, Paul-Bonatz-Straße 9-11,

57076, Siegen, Germany Since their opening, carbon nanotubes (CNTs) have been targets of numerous experimental and theoretical studies. A widely used method of obtaining CNTs is based on a process of decomposition of gaseous hydrocarbons in the presence of catalysts. Synthesis of carbon nanostructures by thermal chemical vapor deposition (CVD) using a nickel nanopowders obtained by electric explosion of wire as catalysts was carried out. The experimental modes of synthesis of carbon nanotubes by low-temperature CVD using nickel nanopowders as catalyst have been found for the first time. Experiments have shown that the lower temperature limit is 325°C. Scanning electron microscopy (SEM) studies revealed the existence of a range of temperatures and pressures in which there is no growth of carbon nanostructures. The results of Raman spectroscopy and X-ray analysis showed that samples grown at a lower temperature limit, determined in the course of the experiments have the highest crystallinity. SEM studies using SE2 mode and results of transmission electron microscopy indicate that the synthesized structures are multi-walled carbon nanotubes with the metal clusters inside the channel of the tube. In the course of the studies carried out by us it have shown that Ni NPs obtained under nonequilibrium conditions of electric explosion of conductors have a crystalline structure with a lattice parameter different from the standard. We suppose that the reduction of the lower temperature boundary is associated with increased catalytic activity of EEW nanopowders, which in turn depends on the changes in the crystal structure parameters of Ni nanoclusters.

342

Magnetic Carbon Nanosphere-Based Molecularly Imprinted Polymers for Dibenzothiophene Adsorptive Removal

Qin L1,2, Liu W F1,2, Yang Y Z1,2, Liu X G1,3 ,Hu L Q4

[email protected]; [email protected]

1Key Laboratory of Interface Science and Engineering in Advanced Materials, Ministry of Education, Taiyuan 030024, China

2Research Center of Advanced Materials Science and Technology, Taiyuan University of Technology, Taiyuan 030024, China

3College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, China

4College of Materials Science and Engineering, Taiyuan University of Technology, Taiyuan 030024, China

Air pollution problems such as heavy smog and acid rains caused by the combustion of sulfur-bearing fuels are becoming burning issues in China. Surface molecular imprinting technique provides an efficient way to adsorptive deslufurization, which can not only effectively ease the environmental concerns but also make full advantages of the valuable organic sulfide. In this work, porous magnetic carbon nanospheres (Fe3O4@C) were obtained by solvothermal method and employed as support materials to optimize the solid-liquid separation process after entire adsorption. After that, the surface molecularly imprinted polymers (SMIP) are synthesized on the Fe3O4@C through a series of functionalization, grafting and elution processes with methacrylic acid as the functional monomer, ethylene glycol dimethacrylate as the cross-linker and dibenzothiophene as templete molecules to acquire a deslufurization sorbent. Field emission scanning electron microscopy, transmission electron microscopy, thermogravimetric analysis, Fourier transformation infrared spectrometry, vibrating sample magnetometry and nitrogen adsorption measurement were used to characterize the morphologies and structures of the products. The adsorption performances of SMIP/Fe3O4@C towards DBT in n-hexane solution (0.8 mmol L-1, 298 K) were detected by gas chromatography. The SMIP/Fe3O4@C shows certain adsorption capacity (15.20 mg g-1) and good selectivity over competitive compounds. The better fitted pseudo-second-order kinetic model and Freundlich model indicate that the adsorptions involve mainly chemical interactions and multilayer interactions. Additionally, the SMIP/ Fe3O4@C can be well recycled under magnetic field.

343

Manufacture of Melt Spinnable Graphene Oxide Liquid Crystal in Aromatic Hydrocarbons

Choi, G.B1, Yang, K.S1, Kim, S.O2

[email protected]

1 Chonnam National University, Gwangju, South Korea 2 Korea Advanced Institute of Science and Technology, Daejeon, South Korea

The Graphene Oxide (GO) has various oxygen functional groups which have strong

physical attraction with solvent. It is difficult to make concentrated solution owing to gelation phenomenon over 1 wt%. Accordingly the carbon fiber from the low-concentration can not be expected the properties of high strength, modulus and conductivity.

To introduce melting property and highly oriented carbon fiber, we applied aromatic hydrocarbons such as coal tar and fluid catalytic cracking decant oil (FCC-DO) intercalation in GO showing mesophases. The residual oils were dissolved in organic solvent and blended with GO dissolved in the same solvent. GO and the residual oils were homogeneously dispersed through the van der Waals interactions among them. The solvent applied for this study were tetrahydrofuran, cyclohexane and benzene.

As residual oils intercalated in GO by van der Waals interactions formed ordered structures and could be spinnable through melt spinning process.

344

Measurement of Graphene Surface Activity by AFM Probe

ZHANG, JY1, JIN, YZ1*, CHEN, J1, FU, QS1, ZHOU, XS2

[email protected]

1 Sichuan University of Science and Engineering, Zigong, China 2 China Rubber Group Carbon Black Research & Design Institute

Graphene as a new carbon material has high specific surface area, excellent mechanical, electrical and thermal properties. The properties of graphene are related to its specific surface activity and surface microstructure. And the study of the adsorption and desorption force of graphene is a good way to characterize the surface activity, which has a great help to the study of graphene and theoretical supplement. The probe of Atomic force microscope (AFM) can produce the adsorption and desorption force signal when it close to and leave away the graphene surface. By this method the surface activity can be measured indirectly. In this paper, the surface morphology and microstructure of graphene were scanned by AFM. Then, the force-distance curve of adsorption-desorption force is constructed to analyse the surface activity of graphene. Finally, the surface functional groups of graphene was tested by Fourier transform infrared (FT-IR). The results show that there are some defects on the graphene surface, which are one of the factors that affect its surface activity. It also reveals that the larger the adsorption and desorption force, the higher the surface activity of graphene. By the FT-IR spectroscopy of graphene it can be seen that surface functional groups have a certain effect on its surface activity.

345

Mechanochemical Friedel-Crafts-Alkylation - a sustainable pathway towards porous organic polymers

Troschke, E1, Grätz, S1, Borchardt, L1



The UN Climate Change Conference 2016 clearly emphasized that the decarbonisation of industry and worldwide traffic is mandatory to stop global climate changes. A chemical approach towards decarbonisation is to remove the greenhouse gas CO2 from the air since its anthropogenic emission is one of the major reasons for global warming. Porous organic polymers like covalent triazine frameworks (CTFs) feature preferred adsorption of CO2 over other gasses. However, classical CTF syntheses are neither economically nor ecologically favourable, hugely suffering from a lack of scalability and the requirement of aromatic nitriles.

Here we demonstrate the synthesis of CTF materials in a solvent-free, mechanochemical approach on a larger scale using abundant and cheap monomers. Different electron-rich and electron-poor aromatic compounds (e.g. carbazole as a model system) were used for CTF synthesis. The influence of different milling materials on the reaction was tested and the successful network formation was confirmed by FT-IR and 13C CP-MAS NMR spectroscopy. The elemental analysis further supports the network formation since C and N-ratios are close to the ideal values. The reaction kinetics were investigated applying an advanced milling setup allowing the in-situ monitoring of pressure and temperature developments inside the milling chamber. Argon physisorption measurements reveal surface areas of up to 600 m2 g-1 for the obtained porous polymers.

Summing up, we performed a mechanochemical synthesis of porous CTF material for the first time. Our process is time-efficient, scalable and enables the usage of readily available and inexpensive educts.

346

Mechanochemical synthesis of nitrogen-doped porous carbon for electrochemical energy storage

Schneidermann, C1and Borchardt, L1



Porous carbons materials have gained vast importance over the last years for energy- and environmentally-relevant applications especially as electrode materials in batteries and electrochemical capacitors.[1,2] In industrial applications, activated carbons are still the most common used materials, but they often cannot fulfill the increasing demands for high energy and power densities. The insertion of nitrogen functionalities into the carbon framework has demonstrated to improve the electrical conductivity, the capacitance behavior, and the wettability of the electrodes with the electrolytes in capacitor applications.[3,4] Conventionally, classical syntheses for N-doped carbon materials effort multiple time-consuming reaction and process steps, and more critically, they accumulate large amounts of waste particularly solvents. Therefore it is a major target to developing new synthesis approaches that reduce the accumulation of solvent waste. Mechanochemistry offers an alternative that allows to carry out reactions in the total absence of any solvent.[5] Moreover, it allows for short reaction times, high yields, and easy scalability.[6] Here we present a mechanochemically-induced one-pot synthesis for nitrogen-doped porous carbons materials from sustainable and cheap precursors by the use of mechanical energy provided by a ball mill. In detail, N-doped carbons are prepared by mechanochemical treatment and carbonization of a mixture of lignin, urea and K2CO3. The resulting Ndoped porous carbon offers a very high specific surface area up to 3000 m2g-1 and large pore volume up to 2 cm3g-1. Moreover, they show superior performance as electrode materials in electrochemical double layer capacitors as compared to non-doped materials and commonly used activated carbons. [1] L. Borchardt, M. Oschatz, S. Kaskel, Mater Horiz 2014, 1, 157–168. [2] L. Borchardt, M. Oschatz, S. Kaskel, Chem. - Eur. J. 2016, 22, 7324–7351. [3] W. Shen, W. Fan, J Mater Chem A 2013, 1, 999–1013. [4] E. Frackowiak, Phys. Chem. Chem. Phys. 2007, 9, 1774. [5] S. L. James, C. J. Adams, C. Bolm, et al., Chem Soc Rev 2012, 41, 413–447. [6] S. Grätz, L. Borchardt, RSC Adv 2016, 6, 64799–64802.

347

Microstructural properties impacting mechanical strength of PAN based carbon fibres.

Fox, D1, 2, Lynch, P1, 2

[email protected]

1 Deakin University, Geelong, Australia 2 CSIRO, Geelong, Australia

Direct measurement of the microstructure properties impacting the mechanical strength of PAN based carbon fibres is investigated. A unique monofilament/multifilament loading system has been designed to examine a fibres microstructural response under various loading configurations. As fibres are incrementally loaded to fracture, both mechanical and microstructural information is captured. Mechanical properties are returned via precise strain measurement using a precision laser distance gauge (displacement sensitivity 0.5µm) while the imposed stress is measured using a 0.25lb load cell. In addition, the fibre microstructure is then revealed by simultaneously recording the Small Angle X-ray and Wide Angle X-ray patterns during loading. First results are presented for the initial PAN precursor fibre and the final carbon fibre processed using the multi tow carbon fibre line at Carbon Nexus research and production facility (Institute for Frontier Materials, Deakin University, Geelong). This will allow us to better understand the carbonization and fibre process strengthening mechanisms with the aim to assist and improve the properties of carbon fibre.

348

Microstructures and tribological properties of C-TaC nanocomposite coatings by CVD

Zhaoke Chen, Xiang Xiong, DongZhe Lv, Yue Li, Wei Sun, Yalei Wang.


State Key Laboratory of Powder & Metallurgy, Central South University, Changsha, Hunan Province, China,410083

Nanocomposite coatings with high wear resistance and low friction is one of the hot subjects. In our group, C-TaC nanocomposite coatings were prepared on graphite substrate by using chemical vapor deposition with TaCl5-C3H6-Ar system. The effects of deposition temperature, the partial pressure of C3H6, and the high temperature treatment on the microstructure and tribological properties of the nanocomposite coatings were investigated.

The results show that, the obtained nanocomposite coating is isotropic, with no obvious preferential orientation, in which the carbon phase is mainly composed of sp2 and sp3 hybridized bond. As the deposition temperature increasing from 900 oC to 1200 oC, both of the grain size and the content of TaC crystallites were increased. The addition of TaC can promote the formation of carbon phase with more SP2 hybrid carbon bonds.

With the increasing of the partial pressure of C3H6, the content of carbon phase increased correspondingly, while the size of TaC decreased gradually. When the mass fraction of C in the coatings was 86.4%, the coating showed a composite structure with the carbon-based coating embedded with nanometersized TaC crystallites.

Heat treatment can increase the content of SP2 hybridized carbon bond in the nanocomposite coating, and then the degree of graphitization of the carbon-based phase. As a result, the nanocomposite coating showed a low friction coefficient of only 0.13, and a very smooth curve of the friction coefficient with time. The main wear mechanism is abrasive wear, adhesive wear and fatigue wear.

349

Microwave assisted synthesis of graphene-Bi8La10O27-Zeolite nanocomposite with

efficient photocatalytic activity

Yonrapach Areerob, Won-Chun Oh*

Email : [email protected]

Department of Advanced Materials Science & Engineering, Hanseo University, Chungnam 356-706, South Korea

Microwave assisted process of synthesis of graphene-Bi8La10O27-Zeolite (G-Bi8La10O27-Z) nanocomposite is being reported first time. In this investigation, a novel route to study on synthesis, interaction, kinetics and mechanism of hybrid G-Bi8La10O27-Z nanocomposite using microwave assisted method has been reported. The photocatalytic activities of as obtained catalysts were assessed based on the degradation of Rhodamine B (RhB), Methylene Blue (MB) and Texbrite (TXB) under visible light irradiation. The results show that the G-Bi8La10O27-Z nanocomposite exhibits an enhancement and acts as stable photoresponse degradation performance under the UV light radiation better than pure G-Bi8La10O27-Z It is evident that the synthesized G-Bi8La10O27-Z can be used as a high performance catalyst for dye waste waters. Moreover, the detailed photocatalytic mechanism of the photodegradation process discussed.

350

Microwave-assisted synthesis of C-doped TiO2 and ZnO as solar-cells electrodes Rangel-Mendez, R1, Matos, J2, Cházaro-Ruíz, L1, González-Castillo, A1, Barrios-Yáñez,

G1


1 Instituto Potosino de Investigación Científica y Tecnológica, San Luis Potosí, México 2 Biomaterials Department, UDT, University of Concepcion, Concepcion, Chile

In this work C-doped TiO2 and ZnO materials have been prepared by microwave-assisted solvothermal synthesis. Microwave-assisted processes permit to reduce the time of reaction and more importantly a better control of the morphology and texture of the samples. In this sense, a systematic study of the influence of the temperature and time of reaction in the synthesis of C-doped TiO2 and ZnO hybrid spheres by using saccharose as carbon source, and titanium isopropoxide and zinc acetate for the semiconductors was performed. Quantum-dots sensitized TiO2 and ZnO spheres were obtained by controlled calcination steps of the precursor hybrid materials. Characterization of the quantum-dots TiO2 and ZnO spheres was performed by adsorption-desorption N2 isotherms, XRD, XPS, SEM, UV-vis/DR and electrochemistry properties. The samples obtained present an important red-shift in the energy band gap of the semiconductors with values of 3.05 eV and 3.13 eV for TiO2 and ZnO, respectively, clearly lower than those on bare semiconductors, which is associated with the C-doping effect. Our results allow to conclude, that the present materials have a potential application as quantum-dots sensitized solar cells.

351

Milk Powder Derived Bifunctional Electrocatalysts for Rechargeable Zinc-Air Battery

.Xuncai, Chen1, Shengli, Zhai1, Li , Wei1, Yuan, Chen1

[email protected]

1 University of Sydney, Sydney, Australia

A bifunctional electrocatalyst was developed for oxygen evolution reaction (OER) and oxygen reduction (ORR). Overdue milk powder is an abundant biomass waste which contains both nitrogen and phosphate. The bifunctional catalyst was prepared by a hydrothermal process, in which N,P co-doped carbon microspheres derived from overdue milk powders are coated with NiFe oxide nanoparticles. The bifunctional electrocatalyst exhibits low onset potent, high current densities, small Tafel slopes, and excellent stabilities for both OER and ORR in terms of low overpotential (338 mV at 10 mA cm-2) for OER, a positive onset potential (0.89V) for ORR, and a stable current density retention for at least 10 h. Detailed mechanism studies suggested that the high activities for OER and ORR can be attributed to NiFe oxide nanoparticles and N,P-co-doped carbon microspheres, respectively. To demonstrate the practical application of this catalyst, a rechargeable Zn-air battery was assembled using the NiFeO/N,P-co-doped carbon microsphere as the bifunctional cathode catalyst. This battery demonstrated an open-circuit potential of 1.35 V, a specific capacity of 688 mAhg-1 (corresponding to an energy density of 811 Wh/kgZn), and can be cycled stably for more than 25 cycles at 5 mAcm-2. This work shows a promising approach of utilizing biomass waste materials to achieve efficient energy conversion and storage.

352

Modification of Reinforcement and Anti-oxidization for Hyperporous Carbon-Bonded Carbon Fiber (CBCF)

Shi J J, Feng Z H, Zhang D H, Yang Y H, Wang Y, Li T, Xu L


Aerospace Research Institute of Materials & Processing Technology, Beijing, China

Carbon-bonded carbon fiber (CBCF) composite is a super lightweight good insulation constituted by chopped carbon fibers, which are bonded by pyrolytic carbon. Because of its porosity and lightweight, CBCF is very easily oxidized at high temperature, and has pure mechanical properties. Herein, we introduced thin SiC ceramic layers onto the chopped carbon fibers in the CBCF low density carbon/carbon composite by preceramic polymer infiltration pyrolysis (PIP) and chemical vapor infiltration (CVI). Under well control of the infiltrated solution concentration and the pyrolysis processing, carbon fibers in the CBCF were uniformly coated by the SiC layer which was about 600 nm thickness through five times PIP processing. Introduction of SiC layers onto the carbon fiber can highly enhance the mechanical performance and effectively protect the CBCF from the oxidization at high temperature. The compressive strength of SiC/CBCF after five times PIP processing was significantly improved from 0.222 MPa of original CBCF to 0.844 MPa through the thickness direction. Meanwhile, the oxidization resistance of CBCF coated by SiC layers was apparently improved, whose initial decomposition temperature was increased up to 800 from ca. 400 of original CBCF. For the modification of reinforcement and oxidization resistance for CBCF, CVI method was also a much more facile way to deposit a thin ceramic layer onto carbon fibers in the CBCF composite. The mechanical properties and oxidization resistance were also remarkably enhanced by inducing SiC ceramic layers through CVI method.

353

Modifications of carbon surfaces pH in aqueous supercapacitor

Slesinski, A, Frackowiak, E, Fic, K



This work presents a unique strategy aiming at extending the operational voltage range in carbon/carbon supercapacitors operating in a neutral, aqueous electrolyte solution (1M Li2SO4). In-depth analysis of the equilibria at the carbon/electrolyte interfaces confirmed the possibility to reach 1.8 V with excellent reversibility during cycling. To reach the goal, the donor - acceptor nature of carbon electrodes has been taken into consideration. Controlled oxidation for positive electrode and ammonia adsorption on negative electrode have been realised to adjust the optimal equilibrium conditions - nitric acid oxidation of carbon leads to the formation of electrochemically active acidic sites. Furthermore, ammonia adsorption promotes an alkaline character in the porosity of the electrode once contacted with aqueous electrolyte solution. Such modifications resulted in the self-controlled pH polarisation in the capacitor system, responsible for higher overpotentials of solvent decomposition. This, in turn, allows capacitor operation at higher voltages. Furthermore, this configuration eliminates the use of physical separation methods (such as an ion-exchange membrane) to decelerate mixing of ions and improves the power denisty of the device.

354

Molecular sensitivity and selectivity of metal nanoparticles decorated graphene as ‘smart’ surface-enhanced Raman scattering (SERS) platforms

Gupta, S1,*, Banaszak, A1, Smith, T1

* [email protected]


Kentucky University, Bowling Green, KY 42101, USA

Graphene-mediated surface-enhanced Raman scattering (G-SERS) is a recent phenomenon that produces clean and reproducible Raman signals of chemical molecules with significantly enhanced intensity in contrast to traditional surface- (SERS) and tip- enhanced Raman scattering (TERS). While SERS and TERS enhancement arise due to electromagnetic mechanism, GERS also relies on a chemical mechanism and therefore it shows unique molecular sensitivity and selectivity. In this work, we developed graphene materials decorated with noble metal (silver and gold) nanoparticles for detection of different chemical molecules, methylene blue (MB) and rhodamine 6G (Rh6G) keeping in view of their optical and biological importance. The results illustrate that silver and gold nanoparticles immobilized on graphene and its derivatives (graphene oxide and reduced graphene oxide) significantly enhance the signal, in general, and as cascaded amplification of SERS signal on multilayer architecture, in particular, larger than those on the metal nanoparticles in absence of graphene. Additionally, the sensitivity can be tuned by controlling the size of nanoparticles. Moreover, highly-sensitive graphene-nanoparticle sensors are capable of molecular detection over 10 pM to 100 M concentration. The G-SERS enhancement is discussed in terms of 1. molecular structures (molecular symmetry; face-down and edge-on and substituents similar to graphene), 2. charge-transfer interaction between molecules and graphene and 3. graphene-metal nanoparticle interfacial hybridization. They are found to be favorable for Raman signal enhancement and corroborated with UV–vis absorption spectra of molecules in contact with or in presence of graphene helping to guide molecular detection useful in medicine and biotechnology.

355

Narrow-diameter Distributed Single-walled Carbon Nanotubes Grown from Carbon Nanorings

Tojo, T.1, Inada, R.1, and Sakurai, Y.1


1Toyohashi University of Technology, Toyohashi, Aichi, Japan.

Our approach to fabricate single walled carbon nanotubes (SWCNTs) with a restricted chirality relies on utilizing carbon nanorings such as cycloparaphenylenes (CPPs) which are the fundamental unit of armchair type SWCNTs (a-SWCNTs). In order to obtain long cylindrical structures from CPPs, well-aligned CPP molecules with various fullerene catalysts on a silicon substrate were pyrolyzed under the ethanol gas flow at 500oC with ultraviolet laser irradiation. In the case of CPP-C84 composites, the pyrolyzed CPPs were observed in transmission electron microscope (TEM) images to be transformed from nanorings to both cylindrical and one-dimensional amorphous structures. Cylindrical structures possessed diameters of 1.5-1.7 nm corresponding to the employed diameter of CPPs even though the amorphous structures were 6-10 nm in short-transverse length. The structural variation could be explained by the difference of the binding arrangement of CPPs under pyrolysis process using fullerene catalysts. The Raman spectra displayed three peaks of D, G-, and G+ bands at 1350, 1570, and 1600 cm-1, respectively, derived from vibration modes of SWCNTs, as well as the radial breathing mode (RBM) at 200 cm-1 without vibration modes of a CPP and fullerene. Therefore, the pyrolyzed CPPs are indicated to include SWCNTs without the presence of non-pyrolyzed CPPs. This also suggests that CPPs are useful for the structure-controlled fabrication of a-SWCNTs.

356

New Evolution of Carbon Nanomaterials for Various Applications

Z.A. Mansurov

[email protected]

Institute of Combustion Problems, Almaty, Kazakhstan Al-Farabi Kazakh National University, Almaty, Kazakhstan

Nanotechnology is one of the most actively discussed directions of scientific and technological investigations which is being highly developed in the recent years and on which the hopes of a wide circle of scientists and technologies anchor their hopes. The paper reviews new scientific results for synthesis and application of carbon materials. The hydrophobic sponges were obtained by coating polyurethane and melamine sponges with carbon nanomaterials. They are excellent water-resistant sorbents for oil, petroleum products and other organic liquids of various densities. Another interesting development is concerned to the synthesis of multiwalled carbon nanotubes on a glass-cloth by use of cobalt oxide catalyst nanoparticles obtained by solution combustion and production of the smart-textile on its basis. A model of soldier with heated jacket based on electroconductive smart-textile was made. The textile showed good electroconductive properties and effective Joule heating by externally applied current. Studies on the development of nanostructured carbon materials and their application as high-performance active components for the electrodes of advanced energy storage systems, in particular electric double layer capacitors were carried out. 2D heterostructures based on graphene and dichalcogenides of transition metals were derived. The epitaxial and single crystals of graphene were synthesized by the CVD-method separately on a copper foil.

357

NH4FeF3/Carbon-Nanosheet Composite as a Potential Anode Material for Li-Ion Storage

Kong, M1, Zhou, J1, 2*, Chen, X1, Song, H1, 2*

[email protected]

1 State Key Laboratory of Chemical Resource Engineering, Beijing Key Laboratory of Electrochemical Process and Technology for Materials, Beijing University of

Chemical Technology, Beijing 100029, P. R. China 2 Changzhou Institute of Advanced Materials, Beijing University of Chemical

Technology, Jiangsu, P. R. China

Transitional metal fluorides (TMFs) are receiving increasing attention as promising electrode materials for lithium-ion batteries (LIBs) due to their resource abundance, low-cost and high specific capacities. However, TMFs usually suffer from lower electron conductivity and higher Li-ion diffusion resistance, which leads to rapid capacity fading. In order to further improve electrochemical performance, paying special attentions to crystal topologies of TMFs and exploring novel structure of TMFs/carbon composites are greatly needed. Here, NH4FeF3/carbon nanosheets (NH4FeF3/CNS) composites were prepared via in situ co-pyrolysis of ferric acetylacetonate and NH4F. It was found that the NH4FeF3 owns interesting cubic perovskite structure, in which FeF6 octahedral monomers are connected with each other via F- anions to form cavities, and NH4

+ cations reside inside the cavities. The interesting perovskite structure is favorable for Li-ion storage. When used as anode for LIBs, the NH4FeF3/CNS composite exhibits the specific capacity of 799 mA h g-1 at a current density of 500 mA g-1 after 300 cycles, which is much higher than that of reported iron fluoride. The better rate-performance and excellent cyclic stability, on one hand, should be ascribed to that the open framework of NH4FeF3 with NH4

+ fillers enlarge the electronic channels so as to make the tunnel-like channels electrochemically stable, on the other hand, should be attributed to that carbon nanosheets can act as a conductive network to improve the conductivity of NH4FeF3 nanoparticles.

358

Nitrogen Tunable Graphene Quantum Dots from Polyacrylonitrile-based Carbon Fibers

Dawon Jang1,3, Byung Joon Moon2, Sukang Bae2, and Sungho Lee1,3


1 Carbon Composite Materials Research Center, Korea Institute of Science and

Technology, Wanju-gun, South Korea 2 Applied Quantum Composites Research Center, Korea Institute of Science and

Technology, Wanju-gun, South Korea 3 Department of Nano Material Engineering, Korea University of Science and Technology,

Daejeon, South Korea

Graphene quantum dots (GQDs) display unique electrochemical and opto-electrical properties due to quantum confinement effect and edge effect. Further, through heteroatom doping, various properties can be endowed to GQDs and thus they can be utilized in various advanced device applications. In this study, nitrogen doped GQDs (N-GQDs) were synthesized by one-step process via solvothermal treatment of polyacrylonitrile (PAN)-based carbon fibers (CFs) containing nitrogen atoms. As PAN-based CFs heat-treated with varied temperatures exhibit differentiated nitrogen content as a function of post heat treatment temperature, nitrogen content of N-GQDs, which are derived from heat-treated PAN-based CFs, can also be easily controlled by simply tuning annealing temperature of precursor PAN-based CFs. According to x-ray photoelectron spectroscopy (XPS) results, N contents of N-GQDs increased as decreased treatment temperature of CFs. From the photoluminescence (PL) analysis, it was observed that the optical properties of N-GQDs could be successfully modulated as a function of nitrogen content. When N-GQDs were applied as an anodic buffer layer in organic photovoltaic (OPV) cells, the power conversion efficiency (PCE) increased from 7.5 to 8.5%. The N-GQDs can be used in various applications due to cost-effective fabrication process, non-toxicity, wide band gap and high solubility.

359

Nitrogen-doped carbon materials analyzed by XPS

Haruki, T1, Yasuhiro, Y1, Satoshi, S1, Shingo, K2


1 Chiba University, Chiba, Japan 2 Kagoshima University, Kagoshima, Japan

Various properties of carbon materials have been improved by introduction of nitrogen. The types of nitrogen-containing functional groups play a crucial role to improve those properties, but the detail analysis of nitrogen-doped carbon materials has not been conducted. X-ray photoelectron spectroscopy (XPS) has been well utilized to analyze nitrogen-doped carbon materials. Nitrogen-containing functional groups are classified into pyrridinic, pyrrolic, amine (C-NH2), and either graphitic/quaternary nitrogen or basal amine. But these functional groups could be classified into more types depending on surrounding environments. In addition, it is well known that most nitrogen-containing raw materials generate large full width at half maximum of N1s XPS spectra because of the formation of unclear functional groups during carbonization. In this work, nitrogen-doped carbon materials with various amine groups were constructed as model structures. C1s and N1s XPS spectra of those structures were simulated by density functional theory calculation and application of scaling factors studied in our group. Peak positions of amine groups such as C-NH2 and basal amine/ graphitic nitrogen have been reported. At the present, we revealed N1s XPS peak shifts of various amine groups depending on surrounding environment. In addition, structural changes of nitrogen-containing functional groups upon carbonization of aromatic compounds were analyzed by peak separation of C1s and N1s XPS spectra.

360

Two-Dimensional Nitrogen-Doped Carbon Nanosheets Supported NiSe2 Nanoparticles as Anode Materials for Enhanced Sodium Storage

Liu, S1, Zhou, J1, 2*, Chen, X1, Song, H1, 2*

[email protected]

1State Key Laboratory of Chemical Resource Engineering, Beijing Key Laboratory of Electrochemical Process and Technology for Materials, Beijing University of Chemical

Technology, Beijing, P. R. China 2Changzhou Institute of Advanced Materials, Beijing University of Chemical Technology,

Jiangsu, P. R. China

Recently, transition metal selenides (TMSs) have gained increasing attention as anode materials for sodium ion batteries (SIBs) because of their high theoretical capacity and superior rate capability. However, TMSs suffer from large volume changes during charge/discharge process, which leads to rapid capacity fading. Therefore, design of the TMSs with high cycling stability is still a great challenge. In this work, a novel nitrogen doped carbon nanosheets supported NiSe2 nanoparticles (NCNs-NiSe2) was synthesized by a simple pyrolysis of hexamine (HMT)/Ni(NO3)2 mixture followed by a simple selenization process. In the as-prepared NCNs-NiSe2, the NiSe2 nanoparticles were uniformly distributed in the two-dimensional nitrogen doped carbon matrix. Meanwhile, the nitrogen doped carbon matrix can significantly improve the conductivity of the composite and buffer the volume expansion of NiSe2 nanoparticles during the charge/discharge process. When served as anode material for SIBs, the novel electrode exhibited a high reversible capacity of 410 mAh g-1

at a current density of 1 A g-1 and still owned a capacity of 310 mAh g-1 after 100 cycles. The excellent sodium storage capability can be ascribed to the synergistic effects of nitrogen doped carbon nanosheets and NiSe2 nanoparticles.

361

Nitrogen-doped CNTs derived from metal–organic framework as efficient ORR electrocatalyst

Rui Li1, Xuzhen Wang1,2,*, Yanfeng Dong2, Lan Yang1, Jieshan Qiu2


1. School of Chemistry, Dalian University of Technology, Dalian, China. 2. Liaoning Key Lab for Energy Materials and Chemical Engineering, PSU-DUT Joint

Center for Energy Research, Faculty of Chemical, Environmental & Biological Science and Technology, Dalian University of Technology, Dalian, China.

Oxygen electrocatalysis is very important for many energy storage and conversion technologies. Replacing noble metal-based electrocatalysts with highly efficient and inexpensive non-noble metal-based oxygen electrocatalysts is a key for the practical applications of these technologies. In this work, a highly active electrocatalyst for oxygen reduction reaction (ORR) was developed by a template induced strategy. The nitrogen-doped carbon nanotubes decorated with cobalt nanoparticles (Co@C-NCNT) composite was derived from ZIF-67 as a precursor and Halloysite nanotubes (HNTs), a hollow tubular structure with deposited hydrated aluminum silicate, as a template. Benefited from one-dimension nanotubes with more exposed active surface area as well as the convenient channels for transport of electrons and reactants, the Co@C-NCNT hybrid exhibits comparable catalytic activity and outperformed durability for ORR, compared with intrinsic nanoparticles by direct carbonization of ZIFs crystals. Additionally, Co@C-NCNT electrocatalyst shows methanol tolerance not only in alkaline solution but also in acidic solution when benchmarked with a commercial Pt/C electrocatalyst. This should be attributed to the synergistic effect from chemical ingredients, particular structure, and optimum N-doping level of the composite. The presented synthesis method for structure-control electrocatalysts would open a new way on preparing promising cathode catalyst candidates for fuel cell applications.

362

Obtaining of Electroconductive Composite Textile Based on Carbon Nanotubes and Glass-Cloth

Smagulova, G,1,2,Tuleibayeva, Sh1,Kim, S1,2,Prikhodko, N1,3, Lesbayev, B1,2, Nazhypkyzy,

M1,2, Zakhidov, A4, Mansurov, Z1,2

[email protected]

1Institute of Combustion Problems, Almaty, Kazakhstan 2Al-Farabi Kazakh National University,Almaty, Kazakhstan

3Almaty University of Energetics and Communications, Almaty, Kazakhstan 4University of Texas at Dallas, NanoTech Institute, Richardson, Texas, USA

In our industrial era, science is firmly integrated with many areas of techniques, particularly in the textile industry, which has led to the creation of a new class of material: smart textiles. Electroconductivetextiles found their wide application and are actively used in a life and technology.In this work presents results of production of electroconductivecomposite smart-textile based on glass-cloth and carbon nanotubes. For obtaining cobalt oxide nanoparticles on the surface of glass-cloth, efficient, cheap, and easy method solution combustion was used. The possibility of using the cobalt oxide nanoparticles as catalyst in the carbon nanotube growth process by CVD process was shown. For investigation the structure and morphology of the carbon nanotubes and glass-cloth-based catalyst with Co3O4 X-ray diffraction (XRD), transmission electron microscopy (TEM) and scanning electron microscopy (SEM) methods were used. Obtained carbon nanotubes have diameter 23-26 nm. Current-voltage characteristics show good electroconductive properties of composite materials - CNT on glass-cloth. Prototype of soldier model with a heated jacket based on electroconductive smart-textile was made. The heating efficiency of the flexible heating element at low temperature was tested. Before connecting to a power source, temperature of the jacket was 0 °C. After connecting to a power source, the temperature of the jacket has increased to 45 °C. Smart-textile based on glass-cloth showed good electroconductive properties and effective Joule heating by externally applied current.This type of conductive glass-cloth with CNT can be used for various functional applications.

363

On the Importance of the Anisotropy in the Polarizability of Carbon Atom for Correct Description of N2 Adsorption on Graphite

Prasetyo, L, Tan, S, Zeng, Y, Do, D. D, Nicholson, D

[email protected]

University of Queensland, Brisbane, Australia

Adsorption of N2 on graphite is often used as a reference for characterization of carbon materials and is commonly studied with a popular model for which N2 is modelled as two LJ sites and three partial charges and its potential energy with graphite is modelled with the Steele 10-4-3 equation. The isotherm simulated with this model fails to describe the transition from the hypercritical state of the adsorbate to the commensurate packing that is observed experimentally in the monolayer region, and it overpredicts the experimental capacity in the multilayer region. Furthermore, it fails to exhibit the spike at the monolayer concentration in the isosteric heat versus loading. To this end, we propose a new model that accounts properly all physical features of graphite: (1) the corrugation of the carbon atoms arranged in hexagonal patterns in a graphene layer, (2) the difference between the polarizability of carbon atom parallel to a graphene surface and that vertical to it, and (3) the different energetic behaviour of the uppermost graphene layer from the underneath layers, modelled with the collision diameter and the well-depth of the energy of interaction of a carbon atom. This new model describes well the adsorption of N2 on graphite – the sub-step in the first layer of the isotherm, the spike in the isosteric heat curve versus loading and the better description of higher layer loadings. The implication of this new model is its long lasting value for better characterization of the pore size distribution of carbon materials.

364

On the Role of Surface Hydrophilicity-Hydrophobicity of Carbon Materials

Hao, G-P1,2, Strasser, P3, Kaskel, S1


1 Department of Inorganic Chemistry, Technische Universität Dresden, Bergstraße 66, Dresden 01062, Germany

2 National Graphene Institute, University of Manchester, Oxford Road, Manchester, M13 9PL, UK

3 Department of Chemistry, Chemical Engineering Division, Technical University Berlin, Straße des 17. Juni 124, 10623 Berlin, Germany

Porous carbons are most popular materials for both academic researches and industrial applications in the field of rechargeable energy-storage systems and catalysis supports due to their features such as high abundance, developed porosity, excellent conductivity and stability. To date, the pore structures of carbon materials can be well tuned, while their surface chemistry is much less controllable, still being considerably hydrophobic surface for most carbon materials.[i] However, applications applied in aqueous conditions (eg, water heat pump, electrocatalysis, etc) require a polar pore surface for effective adsorption of polar molecules or a better wetting.[ii,iii] In this regards, we developed a new family of highly porous carbons with tuneable hydrophilic properties. We systematically examined the relationship between surface hydrophilicity-hydrophobicity and structural features, i.e., surface heterogeneity and pore size. Finally, their applications in water heat pump, supercapacitor as well as CO2 electrocatalysis will be discussed. The insight into hydrophilicity control of carbon materials is helpful to design next generation functional carbon materials for energy storage and heterogeneous catalysts.

365

Optical Fiber Sensors Based on Lossy-Mode Resonance Using Graphene Materials

Sanchez, P1, 2, Hernaez, M1, Zamarreño, CR2, 3, Arregui, FJ2, 3, Mayes, AG1, Melendi-Espina, S1


1University of East Anglia, Norwich, United Kingdom 2Universidad Pública de Navarra, Pamplona, Spain

3Institute of Smart Cities, Pamplona, Spain

Optical fiber sensors (OFS) have attracted increasing attention due to their benefits compared to traditional sensors, such as small size, low cost, biocompatibility, remote sensing ability or safety in flammable environments. Among the different existing configurations of OFS, those based on electromagnetic resonances, such as Surface Plasmon Resonance and Lossy Mode Resonance (LMR) are very popular. When an optical fiber is coated with a thin-film, different electromagnetic resonances can be generated depending on the properties of the materials involved in the system (the waveguide, the coating and the external medium). These resonances produce a stable absorption band in the transmitted spectrum that shifts in wavelength if the refractive index (RI) of the coating varies. Then, if this parameter is sensitive to a determined analyte, the presence of this analyte will lead to a measurable shift of the absorption peak. This is the basis of the sensing mechanism. In particular, LMRs are more versatile and cheaper as they can be supported by a wide range of materials, including metal oxides and polymers. In this regard, graphene-based materials are ideal candidates for the fabrication of the coatings required by LMR sensors due to its superior properties, such as surface area, mechanical strength and extreme sensitivity to the external environment. Consequently, in this work highly sensitive OFS using LMRs and graphene-based materials have been designed and fabricated. This is a new concept and, to the best of our knowledge, the first LMR-based OFS using graphene materials.

366

Oxygen Effect In N-Doped Reduced Graphene Oxides Based Dopamine Sensors

González, Z1, Wiench, P2, Menéndez, R1, Gryglewicz, G2

[email protected]

1Instituto Nacional del Carbón (INCAR-CSIC), Oviedo, Spain

2Wrocław University of Science and Technology, Wrocław, Poland

A series of N-doped reduced graphene oxides (N-rGOs) were proposed as active

materials in dopamine sensors. The examined N-rGOs were synthesized by hydrothermal reduction of graphene oxide (GO) with amitrole (3-amino-1,2,4-triazole) as nitrogen dopant. Controlling the experimental parameters (mainly the temperature and time of reduction), three N-rGOs with different oxygen content were obtained. Thus, the reduction of GO at 150 °C for 2 h (N-rGO-150-2) and 180 °C for 8 h (N-rGO-180-8) resulted in samples with values of 11.9 and 9.4 at.%, respectively as measured by XPS. Additionally, N-rGO-180-8 was annealed at 700 °C in ammonia to obtain a graphene material (N-rGO-180-8/NH3) with an oxygen content of 2.3 at.% ). The electrochemical performance of the as obtained N-rGOs as active materials in dopamine (DA) sensors was studied on the basis of the different oxygen contents measured. With this aim a glassy carbon electrode (GCE) was modified with the different N-rGOs and used as working electrode in a three-electrode cell for detecting DA by means of DPV measurements. In order to obtain the best sensing parameters, the working pH was also optimized in the three sensors being this value the physiological one (7.4).

Electrochemical results indicate that the oxygen content in N-rGO affects important sensor parameters such as sensitivity, selectivity and mainly LOD. Thus the developed sensors exhibited LOD values of 1600, 650, and 400 nM for N-rGO-150-2, N-rGO-180-8 and N-rGO-180-8/NH3, respectively which could be explained considering the high electrical conductivity of the N-rGO with the lower oxygen content.

367

Oxygen Transfer in A Li-O2 Battery: Comparison with Carbon Gasification

Radovic, LR1,2, Salgado-Casanova, A1, Godoy-Gutiérrez, S1

[email protected] or [email protected]

1University of Concepción, Concepción, Chile 2The Pennsylvania State University, University Park, PA 16802, USA

Among the new generation of alkali- or alkaline-earth-based batteries, Li-air and especially Li-O2 have become of great practical interest. Despite the deluge of wide-ranging studies, some of the basic aspects of lithium interactions at the electrode surface are either unknown or quite puzzling. Our approach is to use computational quantum chemistry in an effort to understand the oxygen-transfer processes on the surface of ubiquitous carbon electrodes. In particular, we take full advantage of the (too often neglected) knowledge of alkali- or alkaline-earth-catalyzed carbon gasification, on one hand, and O2 interaction with carbon surfaces, on the other. By pursuing these analogies we argue that a key unresolved issue is the distinction between Li interactions with edge vs. basal-plane surfaces. Thus, for example, in an early study (J Catal 82, 382-394, 1983), we offered circumstantial evidence that oxygen transfer in calcium-catalyzed carbon gasification occurs by virtue of superoxide or peroxide formation, including ‘spillover’ between edge and basal-plane sites. The relevance of such a mechanism, in the light of recent experimental results regarding carbon electrode behavior in Li-O2 batteries, will be reported and discussed.

368

Oxy-Tetracycline Removal Via Ozonation Enhanced with Synthesized Magnetic Carbon Nanoparticles

Kerdnawee, K1, Termvidchakorn, C1, Menakanist, K1, Opasanon, N1, Srisuma,

P1, Suwattanapongtada, N1, Sano, N2, Tamon, H2, Charinpanitkul, T1


1 Center of Excellence in Particle Technology, Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn University, Bangkok, Thailand

2 Department of Chemical Engineering, Graduate School of Engineering, Kyoto University, Kyoto, Japan

Magnetic carbon nanoparticles (M-CNPs) were applied to enhance ozonation of oxy-tetracycline (OTC) which is well-known as contaminated in aquaculture waste water. In this work M-CNPs were synthesized via co-pyrolysis of glycerol and ferrocene with the presence of magnetic induction at 800 °C. Catalytic performance of synthesized M-CNPs for enhancing ozonation of OTC was experimentally examined in comparison with those of other commercial carbonaceous materials, which were carbon black and graphite powder. 100 ppm of OTC was completely degraded within 30 min or two times faster when compared to usage of carbon black and graphite powder. Four-cycle regeneration of spent M-CNPs revealed that OTC removal efficiency in each cycle was almost the same as that of fresh M-CNPs. Such superior catalytic performance of M-CNPs for ozonation of OTC would be attributed to the presence of Fe embedded in M-CNPs. In addition, M-CNPs could be easily separated from waste water by external permanent magnetic because synthesized M-CNPs exerted the AC-magnetic susceptibility Xr,0 of 68.0 g-1, confirming its interaction with magnetic field, which would be useful for its separation.

369

Peptide Self-Assembly as the Aqueous Graphene Interface

Hughes, Z.E.1 and Walsh, T.R.1


1 Institute for Frontier Materials, Deakin University, Geelong, 3216 VIC, Australia

The non-covalent interaction of biomolecules at the aqueous materials interface, including nanoparticles, is of great interest due to potential applications such as material synthesis, biosensing and nano-medicine. These applications have prompted interest in the identification of peptide sequences that can: (i) selectively adsorb to the aqueous graphene interface, and (ii) once adsorbed, self-organise into supra-molecular overlayer structures. However, to fully exploit applications of such peptide-graphene interactions, a molecular-level understanding of these processes at the interface is required. Molecular dynamics simulations, with the ability to predict and reveal interactions at the atomic level, can contribute to the elucidation of the structure/property relationships of such systems. Using our recently-developed polarisable FF in combination with advanced sampling techniques, the likely structures of peptides adsorbed at the aqueous graphene interface are predicted. The adsorption modes of an experimentally-studied peptide, GrBP5-WT (IMVTESSDYSSY), known to have a strong affinity for the basal plane of graphene, is characterised and contrasted against those binding modes of mutant sequences. Furthermore, we apply these state-of-the-art simulations to investigate structures comprising several GrBP5-WT peptide chains adsorbed at the graphene interface, at the aqueous graphene interface at different coverages. We find, in agreement with experimental data, that the GrBP5-WT chains aggregate. The structures of the peptide overlayers is characterised, revealing the factors responsible for driving the aggregation of the adsorbed peptides. Our findings provide insights that will ultimately enable the predictable self-assembly of peptides at inorganic interfaces.

370

Polyaniline-Based Carbon Nanospheres As Anode Materials for Sodium-Ion Batteries

Zhou, C1, Chen, X1, Jia, M1, Zhou, J1, Ma, Z1, Song, H1*

[email protected]


Technology, Beijing 100029, PR China

Currently, sodium-ion batteries (NIBs) have become a promising alternative of lithium-ion batteries (LIBs) for the wide distribution of sodium and similar electrochemical principles. However, the lager ionic diameter of Na+ relative to Li+ becomes the main bottleneck in enhancing the electrochemical performance. Among various anode materials, hard carbon materials exhibit good reversibility and cycling property due to the disorder structure and larger interlayer distance. Moreover, heteroatom-doped carbon materials have been widely investigated for abundant extrinsic defects and increased interlayer distance introduced by heteroatom. However, the rate performance of hard materials in previous reports is desirable to be enhanced. Based on these background, we have prepared polyaniline-based carbon nanospheres (PCSs) by simple pyrolysis of polyaniline nanospheres. PCSs show the high specific capactiy (first charge capacity of 289 mAh g-1 at current density of 50 mA g-1) and excellent rate performance (capacitance remains 139 mAh g-1 at 2 A g-1) which is superior to other carbon electrode materials in literatures. Through the structural characterization and detailed analysis, we consider that the excellent electrochemical performance of PCSs would be due to the high N/O-codoped level (6.27% of N and 14.88% of O), disorder structure and large interlayer distance (0.362 nm) and the distinct superiorities of spherical structure. In a word, synthesis of hard carbon materials with special structure and high heteroatom-doped content is an effective method to enhance the electrochemical capacity of NIBs.

371

Polymer Nanocomposites Based on PETG Containing Carbon Nanoparticles

Paszkiewicz, S1, Szymczyk, A2, Pawlikowska, D1, Irska, I1, Piesowicz, E1


1 West Pomeranian University of Technology, Institute of Materials Science and Engineering, Szczecin, Poland

2 West Pomeranian University of Technology, Institute of Physics, Szczecin, Poland

The poly(ethylene terephthalate-co-1,4-cyclohexylenedimethylene terephthalate) (PETG), is an amorphous thermoplastic polyester that exhibits a glass transition temperature (Tg) of about 80 oC, similar to poly(ethylene terephthalate) (PET). On account of its transparency and clarity, PETG is used in medical, pharmaceutical, and cosmetic packaging. Several studies of PETG based nanocomposites [1-3] confirmed its advantages over many other thermoplastic polyesters. Herein we present how the addition of different types of carbon nanoparticles affects the properties of PETG based nanocomposites prepared by in situ polymerization, i.e. the synthesis of the polymer in the presence of nanofillers. Carbon nanoparticles (CNP) like carbon nanotubes or graphene derivatives forms are multifunctional nanofillers that can play a significant role in increasing the gas barrier properties and, at the same time, decreasing the electrical percolation threshold of polymer films at very low loading [4,5]. The morphological characterization (SEM, TEM) indicated that in situ polymerization is an efficient technique in order to disperse randomly CNP in the whole volume of polymer matrix. References 1.Kalgaonkar R.A. et al., Journal of Polymer Science Part B: Polymer Physics 2003; 41(23), pp. 3102-3113 2. Kalgaonkar R.A et al. Journal of Polymer Science Part B: Polymer Physics 2004; 42(14), pp. 2657-2666 3.Tsai Y., et al., Polymer Composites 2011; 32(1), pp. 89-96 4. Paszkiewicz S., et al. Packaging Technology and Science (subm.) 5. Paszkiewicz S., et al., Polimery 2013; 58, pp. 893-899 Acknowledgments

This work is the result of the research project GEKON2/O5/266860/24/2016 funded by the National Centre for Research and Development and National Fund for Environmental Protection and Water Management, Poland.

372

Polymer Nanocomposites Reinforced with Preformed Porous Single-Walled Carbon Nanotube Architecture

Oh, Y1, Seong, D. G.1, Um, M.K.1, Islam, M. F2


1 Korea Institute of Materials Science, Changwon, Republic of Korea 2 Carnegie Mellon University, Pittsburgh, United States

Since single walled carbon nanotubes (SWCNTs) exhibit exceptionally high Young`s modulus (~ 1TPa) and tensile strength (~ 200 GPa), they have been considered an ideal additive for the reinforcement of the polymer composites. However, most polymer composites reinforced with carbon nanotube have shown limited mechanical improvement which is far below the level of the theoretical performance in consideration of the potentials of CNTs. The poor enhancement of mechanical properties of the composites is ascribed to the fact that the SWCNTs are easily bundled by strong van der Waals interactions induced by their small diameter. Here, we report giant enhancement of polymer composites in mechanical properties by using the pre-fabricated, porous three dimensional SWCNT architecture which was built with individually dispersed SWCNTs. The isotropic SWCNT network acts as 3D pre-rebar system in the thermoplastic urethane (TPU). The TPU/SWCNT composites show giant enhancements of 40,000% and 9,700 % in tensile modulus and strength compared to those of the pristine SWCNT aerogel and bare TPU control sample regardless of the tensile direction. Additionally, we observe that the excellent dispersion quality of SWCNT network in the composite allowed the sensitive NIR-fluorescence under various tensile strains.

373

Polymerization of solvated C60 crystals under pressure and light irradiation

Gonnokami, H1, Yamamoto, S1, Saeki, T1, Murata, H1, Tachibana, M1

[email protected]

1 Yokohama City University, Yokohama, Japan

Micro/nanocrystals of fullerene C60 have attracted much interest due to their unique morphologies, structures and properties depending on solvents or dopants in C60 lattices. Recently, it was reported that ferrocene (Fc)-doped C60 (C60(Fc)2) nanosheets alternating C60 and ferrocene layers exhibited unique pressure-induced transformation, i.e. reversible polymerizations, in C60 layers at room temperature. The study on polymerization in such layered crystals is of very interest for the controlled polymerization and new planer polymerization. In this paper, we report the pressure-induced transformation of C60(Fc)2 nanosheets and its light irradiation effect. C60(Fc)2 nanosheets were prepared by liquid-liquid interfacial precipitation method with the interface of isopropyl alcohol and C60-saturated toluene solution with Fc. A diamond anvil cell of CLOCK type was used for compression experiment. The pressure-induced transformation of C60(Fc)2 were observed in in-situ Raman measurements at room temperature with a 532 nm Nd:YVO4 as excitation .The excitation laser also served as the light irradiation. The polymerization, mainly one-dimensional (1D) polymerization, in C60 layers occur with increasing pressure. The higher pressure can also lead to the formation of higher-order polymers such as two-dimensional (2D) polymers. The polymerization is reversible with pressure. The pressure-induced polymerization, mainly 1D polymerization, is promoted and stabilized by light irradiation. The photo-induced polymerization under the pressure is irreversible. Similar experiment has been carried out for C60 nanosheets solvated with CCl4. From comparing the results, the mechanism of photo-induced polymerization under high pressure will be discussed in light of structure and solvent.

374

Potential of Carbon Gels in Hydrogen Storage Systems

Czakkel, O1, Nagy, B,2 Bahn, E1,3, Fouquet, P1, Villar-Rodil, S4, Tascón, JMD4, László, K2


1 Institut Laue-Langevin, Grenoble, France 2 Department of Physical Chemistry and Materials, Budapest University of Technology and

Economics, Budapest, Hungary 3 Cavendish Laboratory, Cambridge UK

4 Instituto Nacional del Carbón, INCAR-CSIC, Oviedo, Spain

The potential use of porous carbons and carbon nano-structures for hydrogen storage, in particular, has motivated a large number of researchers in recent years. The adsorption and diffusion of molecular hydrogen in carbon materials is also of fundamental interest in various further fields. In this work, we focus on the hydrogen adsorption properties of carbon gels prepared from resorcinol-formaldehyde resins. To compare the effect of the pore characteristics and the surface chemistry samples were prepared with different drying methods and post carbonization treatments. The carbon gels were characterized by low temperature N2 adsorption/desorption, CO2 adsorption and X-ray photoelectron spectroscopy (XPS). H2 uptake measurements were performed at different temperatures. The mobility of the adsorbed H2 on the surface was studied by neutron spin-echo (NSE) spectroscopy. Our experiments proved that NSE is a very powerful tool to study the surface diffusivity of adsorbed H2, even at low relative coverage. The results reveal that the surface chemistry of the carbon has substantial impact on the surface diffusion properties of the hydrogen, while by changing the pore characteristics of the carbon the hydrogen desorption can be shifted towards significantly higher temperatures.

375

Preparation and Investigation of SWCNT Coatings Suitable for Biosensor Applications

Barkauskas, J., Paklonskaitė, I., Gaidukevič, J., Ramanavičius A., Mikoliūnaitė, L., Genys,

P., Petronienė, J.J., Morkvėnaitė–Vilkončienė, I.

[email protected]

Vilnius University, Faculty of Chemistry and Geosciences, Vilnius, Lithuania

SWCNT coatings (~ 400 nm thickness) on the polycarbonate substrate were prepared having aim to use them as electrodes for amperometric biosensors. These coatings were modified using an additional coverage with graphene oxide (GO) flakes (SWCNT-GO coatings) and subsequent annealing (SWCNT-rGO coatings). Produced coatings were investigated in order to identify their structure, electrical properties, surface chemistry and biocompatibility. Electrical conductivity measurements have shown that SWCNTs in contact with a metal (Ag) behave as Shottky barrier devices. EIS measurements revealed that reduced GO sheets facilitate the electron transport along the annealed SWCNT-rGO coating, and these coatings should be especially suitable for biosensors. Contact angle measurements were used to investigate the surface properties of prepared coatings. AFM and SEM images revealed the characteristic morphology features. Raman spectra confirmed the close contact between SWCNTs and rGO flakes in SWCNT-rGO coatings. Raman imaging technique have shown more even distribution of rGO flakes on the top of SWCNT-rGO coatings after annealing at 160 oC. Experiments using SECM were carried out with SWCNT, SWCNT-GO and SWCNT-rGO using the pristine coatings, as well as coatings immobilized with glucose oxidase, and the latter in the presence of glucose. The results obtained suggest that in the case of immobilized SWCNT-rGO coating a direct electron transfer is observed. The assumption was made that SWCNT-rGO coatings are prospective for the design of efficient and reliable glucose biosensors. Our future work is planned to prepare and test the implantable glucose amperometric biosensors using the SWCNT-rGO coatings investigated in this research.

376

Preparation of Activated Carbon by Pressurized Physical Activation

Yi, H1, Shimanoe, H1, Kim, D, Yu, Y1, Nakabayashi, K1,2, Yoon, S1,2, Miyawaki, J1,2




Activated carbon (AC) is widely used as an adsorbent because of its developed pore

structures and various surface functionalities. To prepare ACs, physical activation using oxidative gasses, such as steam and carbon dioxide, is widely applied in industry. However, the physical activation is not suitable for making the pores uniformly. In addition, the activation yield by the physical activation is typically lower than that by the chemical activation. Recently, we have confirmed that the low activation yield and low degree of pore development of physical-AC are given by an inhomogeneous gasification from the outer surface of the carbon particle and microdomains, which is one of the basic structural units of artificial carbon materials. In other words, an insufficient diffusion of oxidative gasses into a core part of microdomains and particles lowered the activation yield, and caused a widening of the pore size distribution for physical-ACs. In this study, therefore, we tried the physical activation with an application of high pressure to accelerate a diffusion of oxidative gasses into the core part of each carbon particle and each microdomain, and investigated the influence of the pressure application on the pore structure and activation yield of ACs.

377

Preparation of Activated Carbon from Petroleum Coke by Co-Activation Method

Chen G1, Shi L1, Chen Y1, Chen X1, Song H1*

[email protected]


Technology, Beijing 100029, P. R. China

It is well-known that petroleum coke is a good precursor for preparing activated carbon because of its high carbon content, low volatile and ash content. In this work, the high surface area activated carbon (HSAC) is prepared by co-activation method using petroleum coke as carbon precursor, KOH and steam as activator under nitrogen atmosphere. HSAC is characterized by SEM, TEM, XRD and iodine adsorption test. The iodine adsorption value of HSAC with the ratio of carbon/alkali (1:4) is 2143 mg g-1, which is much higher than the activated carbon made by traditional chemical activation method. When the ratio of carbon/alkali is 1:5 the iodine adsorption value of the HSAC is 1832 mg g-1. Owing to the corrosion effect of the steam and the potassium vapor on the pore, we could obtain HSAC with large pore size and high specific surface area. When used as electrode materials of supercapacitors, HSAC possessed the capacitance of 281 F g-1 at current density of 50 mA g-1 after 1000 cycles, with an excellent capacity retention of 99%. The co-activation method provides a deep insight for preparing advanced activated carbon under the condition of less alkali carbon ratio and lower temperature.

378

Preparation of Carbon Fiber Precursor from Low Molecular Fraction of Residual Oil

Im, K.K1, Yang, K.S1,2,3*, Choi, J.S4, and Oh, Y.S4

[email protected]

1Department of Polymer Engineering, Graduate School, Chonnam National University, Gwangju, Korea

2School of Polymer Science and Engineering, 3Alan G. MacDiarmid Energy Research Institute, Chonnam National University, Gwangju, Korea

4 Chemical&Polymer Lab. R&D center, GS Caltex Corporation, Daejeon, Korea

Petroleum residues are by-products of oil refinery, such as ethylene bottom oil (or

pyrolysis fuel oil), fludized catalytic cracking decant oil (FCC-DO) which are applicable for carbon fiber preparations. The polycyclic hydrocarbons, such as coal or petroleum-based pitches transform to optically anisotropic nematic mesophase through molecular size growing in a planar direction and followed by stacking in inert atmosphere near 400 . The molecular size of the FCC-DO is widely distributed as 200-2000 dalton, which cause difficulties in preparation of spinnable mesophase pitches because of volatilization of the low molecular fraction and the coke formation of fraction of high molecular weight fraction in the thermal treatment process.

To avoid the problems from the wide molecular size distribution, we fractionated low size of molecules from the FCC-DO. Synthesis of mesophase pitch was performed in two steps. Firstly, thermal reaction of the low molecular size of FCC-DO was proceeded in an autoclave under H2 or N2 pressure at 5.0 /min to 400 - 430 and held for 240minutes. Alternately, zeolite catalyst was also adopted for reduction of activation energy expecting narrow molecular size distribution.

The reaction products were analyzed of molecular distribution, aromaticity, C/H ratio and softening point. The molecular size distributions were three model shape, 200-400 dalton, 400-650 dalton, 700-900 dalton. The fraction of 200-400 dalton in FCC-DO reduced and increase to 400-650 dalton and 700-900 dalton by pressurized reactions under N2 and H2. The molecular size increases were more effective under N2 than under H2. The product from additional thermal treatment under N2 blowing resulted pitches with softening point of 108 -159 .

379

Preparation of isotropic pitch through co-carbonization of EO and PVC

Liu, JC1, Nakabayashi, K2, Miyawaki, J1,2, Yoon, SH1,2,*


1Interdisciplinary Graduate School of Engineering Science, Kyushu University, Fukuoka,

Japan 2Institute of Materials Chemistry and Engineering, Kyushu University, Fukuoka, Japan

Ethylene bottom oil (EO) has been used as a potential raw material for isotropic pitch based carbon fiber (CF). We have reported the isotropic pitch-based CF with an excellent tensile strength for car-body application using EO as a starting material. Specially developed spinnable isotropic pitch prepared from EO by the halogenation/dehydro-halogenation method could successfully afford CF with better tensile strength compared to an isotropic pitch prepared by simple distillation method. However, there remains much room for improving the preparation method because the handling of the gaseous Cl2 is still troublesome and dangerous. Polyvinyl chloride (PVC) can be decomposed with an evolution of chloride radicals and remaining polyyne-type radical molecules above 250oC. In this study, we examined the PVC as a convenient halogen source on the chlorination/dehydro-chlorination reaction to prepare EO based isotropic pitch. We closely examined the effect of EO pretreatment (heat treat at 270oC and 5% low mass-ratio bromination/dehydro-bromination) on properties of pitch precursor for CF manufacturing. It was found that PVC addition increased the methylene and naphthenic groups of pitch which can induce linear bridges between the condensed aromatic units through the chlorination/dehydro-chlorination reaction. Moreover, the pretreatment of EO was found to be effective to increase a reaction efficiency with PVC.

380

Preparation of lignin based carbon microspheres by reverse phase polymerization

Yu BJ 1, 2, Wang CY 1, 2,*


1 Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, P. R. China

2 Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, P. R. China

Commercial lignin, by-product of enzymatic hydrolysis of biomass for bioethanol production, is used to prepare lignin based carbon microspheres by acetone extraction and reverse phase polymerization. Acetone extraction doesn’t only get rid of ash content but also generate non-etherified phenolic OH groups, non-conjugated carbonyl groups and primary OH in lignin precursor. And the reverse phase polymerization has favorable influence on the morphology, size distribution, surface appearance and thermal stability by coordinating the solid content and the dispersed phase content. The lignin sphere shows smooth surface morphology, narrow size distribution at solid content 0.059 and the dispersed phase content 0.050 and excellent thermal stability by the polymerizing processing and introducing nitrogen functional groups. The mechanism for such lignin sphere was postulated based on the results from elemental analysis, FT–IR spectroscopy, laser particle size analyzer, field emission scanning electron microscope and thermogravimetric analysis. Furthermore, the lignin based carbon microsphere can be obtained by direct carbonization from lignin sphere without pre-oxidization process. Thereafter, it is concluded that the reverse phase polymerization is a meaningful and possible industrial process to prepare lignin based carbon sphere.

381

Preparation of Salacca Peel Based Activated Carbons using Microwave Heating

Arenst Andreas Arie, Hans Kristianto, Jessica Atin and Christiandi Arifin

Department of Chemical Engineering, Parahyangan Catholic University Ciumbuleuit 94 Bandung Indonesia 40141


Salacca Peel, a biomass waste which is abundantly available in Indonesia was prepared into a low-cost activated carbon for the removal of cupper (II) ions from synthetic wastewater. The activated carbon was prepared by a chemical activation method with zinc chloride (ZnCl2) followed by a physical activation using microwave heating at microwave power of 540 W for 25 minutes. The Brunauer-Emmet and Teller (BET) surface area for the prepared activated carbon was 1,797 m2/g. The activated carbons were then tested as adsorbents for removal Cu(II) ions from synthetic waste water by varying the initial concentration of Cu(II) ions. It was found that higher initial metal ion concentration exhibited better on metal ion removal than lower concentration. Adsorption equilibrium of Cu(II) metal ions on salacca peel based activated carbon was investigated by both Langmuir and Freundlich isotherms. Langmuir model fitted experimental data well, with maximum adsorption capacity of 1,263 mg Cu(II)/g activated carbons. Kinetic studies were also conducted using three type of models such as pseudo first order, pseudo second order, and intraparticle diffusion mechanism. Kinetic data was represented better by a pseudo second order compared with other two models. Based on the research results, it can be concluded that activated carbons from salacca peels is a potential,effective and low cost adsorbent for heavy metals Cu (II) adsorption.

382

Preparation of SnOx nanofibers using carbon nanofibers as a template and its application to NIB battery

Koji Nakabayashi1, 2, Sho Yoshida1, Jin Miyawaki1, 2, Isao Mochida2, Seong-Ho Yoon1,

2*


1Interdisciplinary Graduate School of Engineering Sciences, Kyushu University, 6-1 Kasuga-koen, Kasuga, Fukuoka 816-8580, Japan, 2Institute for Materials Chemistry and Engineering, Kyushu University, 6-1 Kasuga-koen, Kasuga, Fukuoka 816-8580, Japan,

One-dimensional nanomaterials have stimulated interest due to their importance in basic scientific research and potential technological applications. Tin oxide is an n-type wide band gap semiconductor and it is being used in a variety of applications such as gas sensors, optoelectronic devices and batteries. In this present work, we have successfully prepared SnOx nanofibers using carbon nanofibers as a template. In addition, we will present application of NIB battery by using SnOx nanofibers.

383

Preparation of Spinnable Mesophase Pitch Using Hyper-Coal as Raw Material

Shimanoe H1, Inoue I2, Hamaguchi M3, Nakabayashi K1, Miyawaki J1, Yoon SH1


1 Kyushu University, Kasuga, Fukuoka, Japan

2 KOBELCO RESEARCH INSTITUTE, Kobe, Hyogo, Japan 3 KOBE STEEL, Takasago, Hyogo, Japan

Hyper-coal (HPC) is a novel resource for high performance synthetic carbon materials

which is prepared by solvent extraction of coal using 1-methylnaphthalene (MN) at 350~430oC under high pressure. HPC is relatively cheap and has low ash and excellent thermos-plastic property. However, the application of HPC has been very limited to coke production, fuel for gasification and additive for binder materials. Our group has endeavored to develop the high utilization of HPC to the areas of the functional carbon materials such as the precursor pitch for isotropic carbon fiber and anodic graphite for Li-ion batteries. In this study, we tried to prepare the spinnable mesophase pitch using HPC as an effective

raw material. To moderate the amounts of alkyl groups and the molecular weight, HPC was hydrogenated at 450oC using tetralin. After hydrogenation, the obtained pitch was effectively solvent-treated and removed the volatile matters to obtaining the spinnable mesophase pitch. Molecular weights and their distribution of pristine HPC, hydrogenated HPC and final mesophase pitch were evaluated by TOF-MS. Hydrogenated HPC has lower molecular weight distribution than that of the pristine HPC.

384

Preparing activated carbon with large surface area by new method

Junpei Yamaguchi, Hisanao Imanishi, Jun’ichi Hayashi, Isao Hasegawa

Department of Chemical, Energy and Environmental Engineering, Kansai University, 3-3-35 Yamate-cho, Suita, Osaka, 564-8680, Japan


Activated carbon shows excellent adsorption ability and is expected to be applied to

energy storage, electric double layer capacitor, etc. We reported that the activated carbon with large specific surface was prepared by chemical activation with K2CO3 and that it was necessary to include nitrogen in the raw material. In this work, we tried to use the raw material (coal) including little nitrogen by mixing nitrogen compound (melamine). The mixtures of coal (Loy Yang), melamine and K2CO3 were heated up to the carbonization temperature (500-1000 ) at a heating ratio of 10 /min and were kept for 60 min at the temperature. The porous structure of the prepared activated carbon was analyzed by using nitrogen adsorption isotherm measured at 77K. The activated carbon with the maximum specific surface area was prepared at 800 and the value was near 2500m2/g. And the specific surface area of the activated carbon prepared by this method was much larger than that of the activated carbon prepared by chemical activation without melamine. And then we investigated the temperature range where melamine and K2CO3 acted effectively as the activating agent. It was found that there were two temperature ranges. One range was below 500 and another range was more than 700 . Thus, the activated carbon having the well-developed pore structure was able to be prepared by using both melamine and K2CO3 as activating agent.

385

Production of high-quality graphene for transparent electrodes and Antenna application

Tran Thanh Tung1, Diana N. H. Tran1, Shengjian Jammy Chen2, Christophe Fumeaux2,

Dusan Losic1

1School of Chemical Engineering, The University of Adelaide, Adelaide, 5005, SA,

Australia 2School of Electrical and Electronic Engineering, The University of Adelaide, Adelaide,

5005, SA, Australia

Presenting author’s e-mail: [email protected] A simple and scalable method to prepare pristine graphene from graphite by liquid phase exfoliation process with sonication using graphene oxide as a dispersant is presented. It was found that GO acts as a surfactant to mediate exfoliation of graphite into GO-adsorbed graphene complex in aqueous solution, from which graphene is separated by an additional process. The preparation of isolated graphene from single to few layers is routinely produced with this method achieving an exfoliation yield of up to 60 % from graphite precursor after 15 h sonication. The prepared graphene production showed a high C/O ratio, low defect, high conductivity, and large lateral size ranging from 5 to 10 µm. This high-quality graphene was used to fabricate a transparent electrode by using spray-coating technique showing a sheet resistance of 668 Ω/sq with a transmittance of 80% after annealing at 350 oC. Furthermore, the as-prepared graphene inks can be prepared a Bucky paper by using a vacuum filtration followed by thermal treatment at 900 °C for 1h under Ar atmosphere. This highly conductive and robust film was used for fabrication of a microwave antenna, which demonstrates an efficiency averaging 79% over the bandwidth from 3.1 to 10.6 GHz. This is the highest reported values for graphene antennas in the microwave region due to the combination of high conductivity, substantial thickness and efficiency-driven antenna design.

386

Progressive Fabrication of Graphene and their Potential Applications

Won-Chun Oh

Email :[email protected]

Department of Advanced Materials Science & Engineering, Hanseo University, Seosan

31962, Korea

Graphene has extraordinary physical and electrical properties, so that it has attracted great interest in different scientific areas in the last years. While graphene is a nanomaterial with high electron mobility and elevated conductivity, it has been reported that bare graphene, graphene oxide with new synthesis methods or the combination with other semiconductor materials can be used as catalyst materials. We examined the photocatalytic activity and catalytic recyclability with some kinds of semiconductor/graphene (binary type) or semiconductor/graphene-TiO2 (ternary type) nanocomposites fabricated with modified chemical and physical methods. The prepared composites were characterized by some kinds of spectroscopic techniques including transmission electron microscopy (TEM), Raman spectroscopic analysis, and X-ray photoelectron spectroscopy (XPS). These graphene-based photocatalysts has a great promise for various material/device applications, including solar cells, standard dyes and commercial dyes decomposition and H2 evolution.

387

Pseudocatalytic Effect of Koh-Activated Rice Husk on Hydroxylamine Nitrate Thermal Decomposition

Atamanov M1,3, Jandosov J1,3, Hori K 2, Kerimkulova A1,3,

Amrousse R2, Chenchik D1,3, Mansurov Z1,3


1 Institute of Combustion Problems, Almaty, Kazakhstan 2Japan Aerospace Exploration Agency(JAXA),3-1-1Yoshinodai,Chuo-

Ku,Sagamihara,Kanagawa252-5210,Japan 3 Al-Farabi Kazakh National University, Almaty, Kazakhstan

The thermal decomposition of hydroxylamine nitrate (HAN), a "green" alternative of fuel/oxidizer formulation to hydrazine nitrate as a rocket propellant in the presence of the high SSA (up to 3000 m2/g) activated carbon obtained via activation of rice husk at 850 оС (RH) KOH AC was investigated. RH is a large scale vegetable unique material, e.g.: it is a renewable, green material with low commercial value. Decomposition of the mixture (HAN spiked with RH-derived KOH-activated AC by 1 mass %) was monitored by electron ionization mass spectrometry (EI MS) at different heating rates (from 16 to 128 K/ min). EI MS analysis of HAN decomposition showed two different pictures, i.e.: intensity of the formation of major gas products (NO, NO2 and H2O) was varied. A possible mechanism of reaction pathways of HAN decomposition with the AC is proposed. Decomposition kinetics of mixture (HAN spiked with the 1 AC mass %) was assessed by DTA – TG thermal analysis at different heating rates. The study was conducted at a heating temperature of system ranging from 297 K to 723 K under nitrogen atmosphere at a flow rate around 100 ml/min in aluminium pans. DTA-TG analysis results showed that the initial temperature of HAN decomposition in the presence of the obtained RH-based AC is comparable to Iridium catalytic effect, e.g.: the effect of 1% AC on initial temperature from 185/86оС vs 1% Ir 185/75 оС.

388

Purification for Ultrapure Carbon Nanotubes and Their Dispersion in Composite

Hyun, Y, Agustina, E, Goak, J and Lee, N*


Hybrid Materials Center (HMC), Department of Nanotechnology and Advanced Materials Engineering, Sejong University, 209 Neungdong-ro, Gwangjin-gu, Seoul 143-747, Korea

Carbon nanotubes (CNTs) produced by catalytic chemical vapor deposition (CCVD) inevitably contain metal impurities where some applications such as Li-ion batteries, and high-voltage power cables, require the ultrapure CNTs. However, some former efforts to eliminate metal impurities from CNTs have drawbacks to be applied to large quantity of CNTs due to environmental pollution and high cost.

This study develops a novel environmentally friendly and low-cost route of removing metal impurities from CNTs to ultrahigh purity by nitrogen-bubbling of chloroform. The raw multi-walled CNTs produced from CCVD process contained as high as 5,133 ppm of metal (Fe, Co, Al, Mg) contents. Liquid-phase chloroform was bubbled by nitrogen gas to be introduced to a glass tube with CNTs loaded inside and reacted with metal impurities to produce volatile metal chlorides. The metal chlorides and unreacted chloroform were collected by a cold trap to prevent harmful substances emission. We obtained the CNTs with the metal content as low as ~12 ppm at 1050C for 15 min. The chlorine-containing carbon layer coated on CNTs during the chloroform treatment was easily removed by nitrogen bubbling of water.

To be applied to the semiconducting layers of high-voltage cables, CNT/EEA (ethylene ethyl acrylate) composites were prepared by a solution blending method. However, since CNTs dispersion in resin was strongly affected by their entanglement, in this study the relation of CNTs dispersion in resin and the composite electrical conductance were investigated. CNTs with three different disentanglement degrees were incorporated to EEA resin and characterized for their electrical properties.

389

PVC addition effect on stabilization of EO-derived isotropic pitch fiber

Liu, JC1, Nakabayashi, K2, Miyawaki, J1,2, Yoon, SH1,2,*


1Interdisciplinary Graduate School of Engineering Science, Kyushu University, Fukuoka,

Japan 2Institute of Materials Chemistry and Engineering, Kyushu University, Fukuoka, Japan

The stabilization process is one of the most important processes in the preparation of carbon fiber (CF) because the stabilization of pitch fiber largely influences on mechanical properties. In addition, the stabilization of isotropic pitch fiber is the very time-consuming and costly process. Therefore, the improvement of oxidation property of isotropic pitch precursor in the stabilization process is very important. In the previous study, polyvinyl chloride (PVC) addition could make molecular structures of isotropic pitch precursor improving oxidation reactivity through additional methylene crosslinking bridges between the condensed aromatic molecules. Moreover, PVC addition could increase the naphthenic functional groups through polyene type Diels-Alder reaction of the pitch molecules. In this study, we examined PVC addition effect on the oxidation property of ethylene bottom oil (EO) derived isotropic pitch fiber. EO derived isotropic pitch fiber was stabilized with a relatively rapid heating rate of 3oC/min to examine the adhesion state of stabilized fiber each other. We also examined the addition effect of PVC on the tensile strength of carbonized fiber. It was found that PVC addition increased the oxidation reactivity of isotropic pitch precursor and improved the adhesion resistance even at a rapid heating rate during stabilization. Furthermore, carbon fibers with higher tensile strength was obtained from the isotropic pitch prepared with PVC addition than without PVC addition.

390

Rational Design of the Carbon Molecular Sieve Membranes with High Gas Separation Performance by Tuning the Structure of Aggregative State

of the Polymeric Precursor

Xu, R.S.1, Li, L.1, Jin, X.1, Wang, C.L.1, Lee, K. R.2, Wang, T.H.1

[email protected]

1 State Key Laboratory of Fine Chemicals, Carbon research Laboratory, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China 2 Center for Membrane Technology, Department of Chemical Engineering,

Chung Yuan University, Taiwan 32023, Taiwan Carbon molecular sieve (CMS) membrane, as a novel carbon-based membrane material with the ultramicroporous structure that can distinguish the size of different gas molecular nearby, shows an excellent gas separation performance and great application potential in gas separation. In the preparation of carbon membrane, the structure and property of polymeric precursors are very critical in the preparation of CMS membranes with high gas separation performance. The desired precursors should have a rigid structure with high free volume.

In this paper, a CMS membrane was fabricated from the novel polymeric precursor of phenolphthalein-based poly (aryl ether ketone) (PEK-C) with high structure rigidity and high free volume. The evolution of ultramicropore and microstructure of PEK-C during pyrolysis and gas separation performance of derived CMS membranes were characterized by DTMA, XRD, PALS, and the variable volume constant pressure method. Results showed that the CMS membranes prepared from PEK-C precursor exhibit an excellent gas separation performance with CO2 permeability as higher as 8111 barrer (1barrer =1×10-10 cm3(STP) cm/cm2 s cm Hg) and CO2/CH4 selectivity of 41.The microporous channels and gas separation properties of CMS membranes could be tuned by controlling the structure of aggregative state of polymeric precursors. The molecular chains of precursors maintained at rubbery state will be beneficial to preparing the CMS membrane With higher CO2 gas permeability and selectivity. CMS membranes derived from PEK-C precursor showed a very attractive and potential application in CO2 capture.

391

Reasearch on turbulence assisted CVI process of C/C composite

Liu, N1, Guo, L1, Li, Y1, Kou, G1, Huo, C1


1 Northwestern Polytechnical University, Xi`an, China

A new method-turbulence assisted CVI-of producing C/C composite material is presented. Our work focuses on the simulation and improve the fluid state of the reactant gas such as methane and hydrogen, in order to provide pressure imbalance between the inside and outside of the carbon fibre preform, thus fasten the exchange among the fresh reactant gas and exhaust gas. The simulated fluid condition was studied and the turbulent induced was quantified by the shape of the graphite model. In the study, turbulence was considered as a “mixer” of the gas to speed up the chemical reaction and the pressure imbalance of the reactant chamber can help to draw away the exhaust gas from the fibre preform. densification process of CVI was studied in detail. The result showed that the turbulence assisted CVI method could produce thicker and denser C/C composite than traditional method in the limited time frame.

392

Refinement of Oxygen Functional Groups of Nanocarbon catalyst

Jiaquan Li1, Peng Yu1, Jie Liu1, Jingxin Xie1, Junfeng Rong1 , Hongyang Liu2, Dangsheng Su2


1Research Institute of Petroleum Processing, Sinopec. Beijing, 100083, China 2Shenyang National Lab for Material Science, Institute of Metal Research, Chinese

Academy of Sciences, Shenyang, 110016, China

Nanocarbon materials are promising catalysts of oxidative dehydrogenation of alkanes, but the improvement of alkene selectivity is still a challenge. Detailed studies on electrophilic peroxides which account for deep oxidation of alkenes were rarely reported. A detailed analysis and evidence for the impact of electrophilic oxygen and phenol groups on ODH of n-butane is presented. By chemical reduction and annealing in N2, peroxide species on oxygen-functionalized CNTs (o-CNTs) are eliminated and the alkene selectivity is significantly improved.We figured out that the amount of electrophilic oxygen is the main factor for combustion side reaction and used iodometric titration method to quantify the amount of electrophilic oxygen on the surface of CNTs. The proposed iodometric titration method, combined with TPD and XPS data, indicates that reduction by LiAlH4 and annealing treatment can both eliminate electrophilic oxygen and carboxyl groups which can be oxidized into peroxides, thus improve the selectivity to C4 alkenes. We showed evidence that in ODH of n-butane, phenol groups play a positive role for catalytic performance since it can be converted to carbonyl during ODH reaction and phenol groups may have the functionality of antioxidants as hindered phenolics. We proposed new strategies to enhance the catalytic activity of CNTs by both inhibiting side-reactions and facilitating new active site formation from phenol groups.

Keywords: carbon nanotubes, catalysis mechanisms, oxygen groups, modification methods, oxidative dehydrogenation

393

Removal of radio-active strontium(90Sr) from seawater by using natural carbo-hydrate polymer composites

Hong, H.-J.1,*, Kim, B.-G.1, Ryu, J.1, Park, I.-S.1, Ryu, T.1, Chung, K.-S.1, Kim, H.2

[email protected]

1Korea Institute of Geoscience and Mineral Resources, Daejeon, South Korea 2Korea Atomic Energy Research Institute, Daejeon, South Korea

The Fukushima nuclear plant accident(2011) has led to serious seawater contamination by radioactive strontium (90Sr). 90Sr isotope is a beta emitter with a half-life of 29 years. It genetically affects seawater organisms and eventually causes damage to humans. Thus, the demand for a 90Sr(II) removal technique from seawater is increasing. To remove Sr from seawater by adsorption technique, highly selective, low-cost carbo-hydrate polymer composites are synthesized and Sr adsorption performance is systematically evaluated in this study. Alginic acid is a polysaccharide from marine brown algae which includes anionic blocks of 1,4 linked -l-guluronic acid(G) and -d-mannuronic acid(M). Due to anionic functional groups as well as Sr concentrate property of alginic acid, alginate exhibits excellent Sr adsorption capacity. Alginate microspheres have demonstrated a superior adsorption capacity for Sr(II) ions (≈110 mg/g). The mechanism of Sr(II) adsorption is inferred as an ion exchange reaction with Ca(II) ions. However, highly concentrated cations in seawater(Na: 10,000 ppm, Mg: 1,200 ppm, Ca: 400 ppm, K: 400 ppm) significantly interfered with Sr(II) adsorption. Also, alginate microsphere is excessively swollen up which is mechanically week in seawater. To overcome the drawbacks of the use of alginate microspheres, following three different alginate based composites are prepared; alginate-magnetite composite, MnO2-alginate bead and zeolite-alginate foam. Improved Sr adsorption performances in seawater, swelling properties of these alginate composites will be presented.

394

Removing Traces of Pharmaceutical Residues onto Activated Carbon Fiber Cloth

Fallou, H1, Giraudet, S1, Cimetière, C, Le Cloirec, P1, Wolbert, D1

[email protected]


Emerging organic contaminants are an increasing concern for the production of drinking water. Traces of these contaminants are often encountered in surface or ground waters used as resources for water supply. Actual treatments are partially efficient to remove these pollutants. In this study, the adsorption of eight micropollutants (pharmaceutical residues, pesticides and plasticizer) was studied at two different scales: batch reactors (10 L) and dynamic conditions (flow rate of 10 L.h-1); and within three aqueous matrices: ultrapure, tap and ground natural waters. Trace concentrations were considered (ng - µg.L-1) and the residual concentrations were determined using UPLC-MS2. On one hand, in batch reactors, kinetics and equilibrium of adsorption were measured. On the other hand, an experimental unit was designed to carry out the adsorption of these micropollutants (inlet concentration of 1 µg.L-

1) in natural water. The breakthrough curves were determined. Different impacts of the natural organic matters (NOM) were enlightened. In batch reactors, large detrimental influences were shown on adsorption capacities (drop higher than 75 % in natural water, containing 2.9 mgC.L-1, in comparison with ultrapure water). In dynamic conditions, the NOM contained in tap water had a negative impact, higher than natural water, which might occur because of the nature of NOM (more hydrophilic and less aromatic compounds). In the natural water, the adsorption capacities were similar to the estimations in batch reactors for four of the contaminants (caffeine, ibuprofen, mecoprop, benzotriazole) whereas negative impacts, attributed to pore blockage, were observed for acetaminophen, diclofenac, carbamazepine, and bisphenol A.

395

Role of graphene on the properties of cellulose fibre/polyester composites

Raza, MA1, Ali, HQ1, Ghauri, FA1, Ahmad, R1, Raffi, M1


1Department of Metallurgy and Materials Engineering, CEET,

University of the Punjab, Lahore, Pakistan 2Department of Materials Engineering, National Institute of Lasers and Optronics,

Islamabad, Pakistan

Cellulose fibre-based polymer composites are light weight, eco-friendly, inexpensive and have potential to be used in automotive, packaging and aerospace industry. However, they have lower strength than synthetic fibre-based polymer composites mainly due to poor interaction of fibres and polymers. The aim of this work was to enhance strength of cellulose fibre reinforced unsaturated polyester (UPE) composites by functionalisation of fibres and by incorporation of small quantities of graphene nanofillers. Functionalised cellulose fibres (FCF) were produced by treating fibres with maleated high oleic sunflower oil to improve dispersion of fibres in UPE. To the FCF/UPE composites, thermally reduced graphene flakes (TRGF), graphene oxide (GO) and thermally reduced graphene oxide (TRGO) were incorporated at 0.1 wt.% to produce hybrid composites. Graphene fillers were synthesised from graphite powder by modified Hummers method followed by ultrasonication or combined thermal reduction and ultrasonication. The graphene fillers and FCF were characterised by atomic force microscopy, Raman spectroscopy, infrared spectroscopy and scanning electron microscope. Graphene fillers were mixed in 3 wt.% FCF/UPE composites by 3 roll milling followed by mechanical stirring to produce hybrid composites. FCF/UPE composite at 3 wt.% loading offered better tensile properties than corresponding untreated cellulose fibre/UPE composite. However, addition of only 0.1 wt.% of GO into the former increased its tensile strength by 65 %. TRGO and TRGF though did not increase strength of composites but they significantly increased elongation of FCF/UPE and reduced brittleness of UPE. The best combination of strength and ductility in FCF/UPE composites was offered by TRGF.

396

Role of Porosity in The Hygroscopic Nature of Nanodiamonds

Piña-Salazar, E-Z1,2, Urita, K3, Hayashi, T4, Osawa, E5, Sakai, T6, Kaneko, K2,*

1 Interdisciplinary Graduate School of Science and Technology, Shinshu University, Nagano, Japan

2 Center for Energy and Environmental Science, Shinshu University, Nagano, Japan 3 Department of Applied Chemistry, Faculty of Engineering, Nagasaki University,

Nagasaki, Japan

4 Department of Water Environment and Civil Engineering, Shinshu University, Nagano, Japan

5 Nano-Carbon Research Institute, Ltd., Ueda, Nagano, Japan 6 Department of Materials Chemistry, Faculty of Engineering, Shinshu University, Nagano,

Japan * [email protected]

Nanodiamonds are found as aggregate structures (50-500 nm) of polyhedral particles of carbon sp3 hybridized atoms, which can be produced as small as about 5 nm in diameter. Each particle is wrapped by graphitic or amorphous carbon layers. Aggregation of nanodiamond particles should have inter-granular gaps which accounts mainly for mesoporosity, microporosity, as well as for ultra-microporosity to less extent. Among many of the potential applications of nanodiamonds, their interaction with water play a significant role. However, so far today, there have been few attempts to analyze deeply the adsorption of water and wettability of nanodiamonds especially linked to their wide range of structures. The study of water adsorption on nanodiamonds, as well as their water-contact angle (35o oxidized and 93o reduced) reveal hydrophobicity of this material despite exhibiting low oxygen-functionalities content. Surprisingly, these aggregates, at bulk scale, quickly absorb water droplets. Such hygroscopic nature may be ascribed to the mesostructure of their aggregates and/or the special rim structure of each nanodiamond particle (hierarchical structure or their wrapping graphitic layer). This work analyzes the dependency of the hygroscopicity of nanodiamonds on their hierarchical porosity evaluated by nitrogen adsorption isotherms. Complementary analysis using X-Ray diffraction, X-ray Photoelectron Spectroscopy and Electron Energy Loss Spectroscopy (EELS by TEM) elucidated the association among these characteristic structures with the hygroscopic property of nanodiamonds. This opens the possibility for their application in water harvesting.

397

Scaled-Up Fabrication Of Porous-Graphene-Modified Separators For Lithium Sulfur Batteries

Huang, JQ1,2, Zhai, PY2, Peng, HJ2, Zhang, Q2




Lithium sulfur battery is regarded as one of the most promising post-LIB

technologies owing to its overwhelming advantage in energy density. However, the dissolution and diffusion of polysulfide intermediates induce undesirable shuttle effect and passivate separator/electrode interfaces.

Herein we reported a facile, scalable, and green process to fabricate porous graphene (PG) modified separators for commercially viable lithium−sulfur batteries. PG, in combination with amphiphilic polymer binder, rendered the engineered functional layer with extraordinary electrical conductivity, high surface area, large pore volume, and appropriate strength of chemisorption to polysulfides. Therefore, lithium−sulfur cells with sulfur loading of 1.8-2.0 mg cm−2 and PG separators exhibited a very high sulfur utilization of 86.5 % (vs. 55.6 % on cell with routine separator) at 0.05 C, a very low self-discharge rate of 90 % retention (vs. 65% retention on routine separator), and enhanced rate capability. In addition, the fabrication of both PG and PG-coated separators was readily scaled-up for assembling and evaluating lithium−sulfur pouch cells with a large areal sulfur loading of 7.8 mg cm−2 and an initial discharge capacity was 1135 mA h g−1 at current density of 0.1 C. This is ascribed the statically and dynamically suppressed shuttle effects of hybrid separators through both the physical trapping of polysulfides onto porous graphene and chemical binding of intermediates on poly(vinyl pyrrolidone) binder in a working cell.

Such concept holds promise for practical applications of lithium−sulfur batteries, and can also be incorporated into other energy storage system based on multi-electron chemistry and regulate the diffusion of intermediates in a working cell.

[1] Zhai, P. Y.; Peng, H. J.; Cheng, X. B.; Zhu, L.; Huang, J. Q.; Zhu, W.; Zhang, Q.

Scaled-up fabrication of porous-graphene-modified separators for high-capacity lithium–sulfur batteries. Energy Storage Mater. 2017, 7, 56-63.

398

Si/Carbon Microspheres＆Graphene Composite as High Stability Electrode for Lithium-Ion Batteries

Jiao, M1, Wang, C1

[email protected], [email protected]

1 Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, P. R. China

The Si/carbon composite material used as lithium ion battery (LIB) anode was synthesized by emulsion polymerization of the mixture of resorcinol and formaldehyde in the suspension of silicon, followed by loading on the graphene sheets and annealing treatment of 800 °C. The structure of the as-prepared Si/RF@G composite is that the Si/RF microspheres are supported on the graphene. In the main portion about Si/RF, some of the Si nanoparticles are embedded into the hard carbon, which can provide the great strength alleviating the volume expansion and shrinkage of Si. The rest of graphene portion enhances the electronic conductivity and also prevents the electrode cracks. Hence, this Si/RF@G composite could not only partly accommodate the volume changes but also perform outstanding electrochemical performances. Compared with the RF and Si/RF samples, the Si/RF@G composite possesses the specific charge capacity of 514.8 mA h g-

1 at the high current density of 2 A g-1 and have the high charge capacity of 818 mA h g-1 at the current density of 100 mA g-1 after 100 charge and discharge cycles. Resultantly, the Si/RF-G composite shows great potential for the application of lithium-ion battery anode material in the future.

399

SiC/SiO2 Anti-oxidation Layer Coated on the Surface of Graphite Spheres

Zhou P, Zhao, HS, Wang TW, Zhang KH, Liu XX, Liu B.


Institute of Nuclear and New Energy Technology, Collaborative Innovation Center of

Advanced Nuclear Energy Technology, Tsinghua University, Beijing 100084, PR China

Graphite is one of the most important material for the reactor core and fuel elements of high temperature gas-cooled reactor (HTR). Improving the oxidation resistance of graphite is very essential for the research of new fuel elements and the development of HTR. In this study, a gradient SiC layer of 500~700 μm was prepared on matrix graphite spheres by a two-step pack cementation, and the outer SiO2 layer prepared by the high-temperature oxidation process. The phases, microstructure, bonding strength and oxidation resistance of coated matrix graphite spheres were investigated. Results show that graphite spheres coated with SiC/SiO2 layer process very good anti-oxidation properties. The SiC/SiO2 coated matrix graphite spheres were carried on rapid thermal shocking tests from 1773 K to room temperature for 50 times without any cracks. The SiC/SiO2 coated matrix graphite spheres exhibits excellent anti-oxidation properties. No obvious weight loss was found after isothermal oxidation in air at 1273 K for 50 h and the weight gain was less than 1% at 1773 K in air for 50 h due to the oxidation of SiC layer.

400

Significantly Improved Solubility of Carbon Nanotubes in Superacids via Purification and their Assembly into high performance liquid crystalline fibers

Jeong, HS, Lee, DM, Lee, JG, Kim, SM

[email protected]

Korea Institute of Science and Technology, Jeonbuk, South Korea One of the most important issues for using carbon nanotubes (CNTs) in a range of applications is transforming individual CNTs into macroscale CNT materials. CNT fiber is one of the promising high performance CNT assemblies. Especially, the liquid crystalline based CNT fiber exhibits superior mechanical, electrical and thermal properties than other CNT fibers due to the nature of liquid crystalline (LC) properties enabling high packing density and alignment of CNTs. Unfortunately, it is difficult to solely disperse CNTs in a desired solvent, eventually preventing highly concentration CNT solution enough to induce lyotropic LC phase. To date, it is believed that only high crystalline CNTs can exhibit lyotropic LC phase based on protonation mechanism in chlorosulfonic acid (CSA) which is known as the only thermodynamic solvent for CNTs. In this study, we show that heat treatment in air, one of the most frequently used purification steps, significantly enhance solubility of CNTs in CSA. It is found that the oxygen-containing groups incorporated during the heat treatment in air serve as specific center for protonation. Based on optimal purification process, the CNTs produced by floating catalyst chemical vapor deposition can be solely dissolved in CSA and highly concentrated. The CNT solution prepared in this manner shows schlieren texture exhibiting nematic phase of CNT LCs, with large domain. The CNT LC fibers produced by typical wet-spinning process exhibits high specific strength (0,84 N/tex), stiffness (115 Gpa) and electrical conductivity (25,000 S/cm).

401

Silicon carbide-derived carbon composites for anode of lithium-ion battery

Cong, Y, Zhang, J, Li, X K, Cui, Z W, Dong, Z J, Yuan, G M, Li Y J


Wuhan University of Science and Technology, Wuhan, P. R. China

Unique silicon carbide-derived carbon (SiC-CDC) coated graphitized mesophase microbead (GMCMB) composites (GMCMB@SiC-CDC) were prepared by solid reaction of GMCMB and silicon and following etching reaction with chlorine. The porous SiC-CDC as the outer shell uniformly covered on the surface of the GMCMB. The microstructure of SiC-CDC was characterized as mainly amorphous carbon combined with some short and curved sheets of graphene. N2 adsorption/desorption isotherms and pore size distributions proved the composites presented both an enormous amount micropores centered at around 0.5~0.6 nm and a few mesopores (2~50 nm). The GMCMB@SiC-CDC composites showed higher specific surface area and pore volume, especially the microporous surface area and volume. The composites as the anode materials manifested much higher charge specific capacities of 877.6 mAh·g-1 at the first cycle compared with pure GMCMB of 359.6 mAh·g-1, which was probable that Li ions could insert into not only carbon layers but also micropores. The GMCMB@SiC-CDC composites presented better cycling performances and discharge specific capacities at higher charge/discharge rates. The component and electrochemical performances of the composites can be optimized through changing the molar ratio of GMCMB/Ti to control the corresponding proportion of SiC-CDC and GMCMB.

402

Silicon@ porous carbon/CNTs Composites for lithium battery anodes

Fu, D J*, Chen, J J, Tan, M L, Zhang, W L, Ma, Q， Wu, w w.

Corresponding author’s e-mail: [email protected]

Research Institute of Tsinghua University in Shenzhen, Shenzhen, China

A novel Silicon@ porous carbon/CNTs composite was prepared by embedding Si nanoparticles coated with a layer of porous carbon in CNTs networks using the spray drying method. The electrode delivered a stable reversible capacity of 800 mAh g-1 after 50 cycles at 100mA g-1, which was much better than that of a si electrode. This can be attributed to the fact that the porous carbon matrix buffers the volume changes of Si nanoparticles, and the CNTs network structure possessing excellent resiliency could keep morphology stability of the composite.

Keywords: anode materials, silicon, carbon nanotubes, lithium ion battery

403

Effects of CNT Composite on Snow Sliding Property and Water Sliding Property on the Vibrated Surface of Silicone/ CNT Composite Sheets

Yanagisawa, K., and Tsuchiya, M.


National Institute of Technology, Nagano College, Nagano, Japan

Vibration has been used to accelerate the velocity of water sliding on a silicone sheet. So far, studies on velocity of snow sliding on silicone sheet were limited. If vibration has an effect on snow sliding on a silicone sheet surface, prevention of accidents caused by falling snow was expected. The aim of the present study was to investigate snow sliding property on the vibrated silicone sheet and the vibrated CNT composite sheet. In this study, the surface functions are controlled using vibration, which can be achieved

in the following processes: 1) A thermosetting silicone resin is selected as matrix material for plastic sheets. 2) Vapor grown carbon fiber (VGCF 2wt%) provide a good mechanical reinforcement potential to the plastic sheets. 3) The jig has vibrated sympathetically. 4) The frequency of the vibration is 100Hz ~ 28 kHz. 5) Snow particle and water droplet behaviours’ were taken with a video camera. 6) The moving distances of snow particle and water droplet were measured. According to the experiments, we obtained following results. Moving distance of snow

particle was increased with the increase in the amplitude. Change of frequency does not affect the moving distance of snow particle. Moving distance of snow particle on a CNT composite sheet was larger than moving distance of snow particle on a silicone sheet. Acknowledgement This work was supported by JSPS KAKENHI Grant Number 15K17962.

404

Surfactant-free solvothermal synthesis of spherical Ni(OH)2-graphene oxide nanocomposite for supercapacitor application

A.A. Khaleed1, A. Bello1, J. K. Dangbegnon1, O. Olaniyan1, K. O. Oyedotun1, F.U.

Ugbo1, D.Y. Momodu1, F. Barzegar1, B. W. Mwakikunga2, N. Manyala1


1 Department of Physics, Institute of Applied Materials, SARCHI Chair in Carbon Technology and Materials, University of Pretoria, Pretoria 0028, South Africa 2

DST/CSIR National Centre for Nano Structured Materials ,Council for Scientific and Industrial Research, P.O. Box 395, Pretoria 0001, South Africa

The growing need for energy coupled with the rise in global warming and air pollution due to the burning and consumption of fossil fuels has led to an increase in alternative energy sources to meet the exponential rise in energy. Electrochemical capacitors also known as supercapacitors have attracted great attention in electrochemical energy storage application resulting from their outstanding work rate, excellent cycle life and moderate energy density. In general, they are classified into two based on the mechanism in which the store charges. Electrochemical double-layer capacitors (EDLCs) that store energy based on ion adsorption, and pseudocapacitors which store energy by the fast surface redox process. Composite of spherical Ni(OH)2/GO was synthesized via a surfactant free solvothermal technique and tested as electrodes for electrochemical capacitors. Structural and morphological analysis confirmed that incorporation of GO into Ni(OH)2 does not change the crystal structure of the pure hexagonal α-Ni(OH)2. Electrodes fabricated from the composite demonstrates a superior electrochemical performance when compared to the pure Ni(OH)2, exhibiting a specific capacity of ∼ 420 mA h g-1, and ∼ 218 mA h g-1 for Ni(OH)2 at 10 A g-1, with a corresponding rate capability of 78% and ∼53 % respectively. The stability study of the Ni(OH)2/GO composite exhibits a good energy efficiency of ∼ 86% at a current density of 5 A g-1 after 1000 charge-discharge cycles.

405

Structural Design and Sodium Storage Properties of Anode Materials Based on Conversion Reactions

Fei, H, Chengzhi, Z, Xuanke, L


College of Materials Science and Engineering, Hunan University, Changsha, China

Currently, sodium ion batteries (SIBs) have increasingly attracted a good deal of research interests for large-scale energy storage systems, mainly because of the rich abundance of sodium resource, low cost and similar chemical properties of sodium and lithium. And the development of new material systems and emerging of novel material engineering methods is hot and difficult problem in the present study. Due to the 39% larger ionic radius of Na ions compared with Li ions, it is a great challenge that how to improve the structural stability and ionic diffusion rate of anode materials for SIBs. Based on the structural design and interfacial modification of nanomaterials, herein, we report the synthesis methods and sodium storage performance of several designed hybrids based on conversion reactions, including carbon-coated CNT@FeP with an amorphous and mesoporous framework, well-dispersed and porous FeP@C nanoplates, carbon-coated CNT/CoS hollow nanostructure and coaxial CNT@CoS@C core-sheath nanowires. The results show that carbon surface modification, 2D nanoplates, amorphous and porous framework and inner hollow nanospheres are promising structural characteristic to improve the insertion/extraction kinetics of ions and make the electrode more tolerant during cycling. Furthermore, comparative electrochemical experimental results and simulated calculations suggest that the sulfide/phosphide-based active species possesses better electrochemical properties in term of reaction reversibility and structural stability than its oxide-based counterpart with similar morphological and structural features.

406

Structural-Changes of the Organic-Binder-Interface According to the Orientation-Plane of Natural-Graphite-Particles

Dong Su Kang, Sang Min Lee, Jae Seung Roh

[email protected].

Kumoh National Institute of Technology, Gumi, Gyeongbuk, Korea.

Bulk graphite is fabricated through the mixture, formation, carbonization, impregnation, re-carbonization, and graphitization of carbon-based raw materials. Carbon-based filler materials including cokes and graphite, which are used as raw materials in the fabrication of bulk graphite, mix appropriately with pitch or resin-based organic binders. Such carbon-based fillers have graphitic crystalline structures. The crystalline structure of graphite is a hexagonal system with an anisotropic structure with covalent bonds in the a and b axis directions and van der Waals bonds in the c axis direction. The characteristics of the interface between the carbon-based filler of the anisotropic structure and the binder are predicted to be a critical factor in determining the quality of the final graphite product. In this study, the interface structure of the organic binder was observed according to the orientation plane of the natural graphite particles with developed anisotropy. The natural graphite particles and organic binder were mixed equally and cured at 70 in order to carry out the observations. The cured specimen was heat treated at temperatures above 500 , which is the binder carbonization temperature, for carbonization. The microstructure of the interface was analyzed for various heat treatment conditions and orientation directions.

407

Structure And Wear Property of Cf/Cu/C Composite under Electric Current

Yin, J1, Zhang HB1, Xiong X1, Yang PA1,Wang P1,Deng, CY1

Presenting author’s e-mail:[email protected]

Central South University, Changsha, PR China

Using carbon fiber needled fabrics with Cu-mesh as the preform, Cu mesh modified carbon (Cf/Cu/C) composites were prepared by chemical vapour infiltration (CVI) with C3H6, impregnation-carbonization (I/C) with furan resin and pitch, respectively. Microstructures and wear behaviours of Cf/Cu/C composites were investigated on a pin-on-disc wear tester under electric current. The results show that microstructures are different from each other. Cf/Cu/C composites with pyrolytic carbon have better combination between carbon fibre, Cu mesh and carbon matrix and also the lowest wear rate and friction coefficient. The wear process of Cf/Cu/C composites with pyrolytic carbon was dominated by abrasive wear.

408

Study of Carbonized Vegetable Raw Material as Absorber for Solar Collectors

Prikhodko, N1,2, Rakhimzhan, N1, Smagulova, G1,3, Lesbayev, B1,3, Nazhipkyzy, M1,3, Temirgaliyeva, T1,3, Mansurov, Z1,3




The main component in determining the efficiency of a solar collector and its value is a selective absorbent coating applied to the outside of the inner tube. Despite the fact that the currently were received selective coatings with a high degree of absorption and low reflectivity, a search for new materials for solar absorbers don't ceases. When was applied absorbent material with absorbent capability to 98% and with practical lack of reflection from it and maximum thermal insulation in the infrared, you can enhance the efficiency of the solar collector to a value above 80%. On this paper presented the results of the study of model samples of the solar collector with an absorber on the basis of carbonized vegetable matter. It is found that the best absorbtion capacity has an absorber based on carbonized rice husk. Analysis of structural and morphological properties of the powder of carbonized material based on vegetable raw materials was performed on the Raman spectrometer (NTEGRA Spectra Raman, λ=473 nm), and scanning electron microscope (Quanta 3D 200i Dualsystem, FEI). The elemental composition was determined at the energy-dispersive x-ray spectroscopy (EDAX). BET analysis of samples was conducted. It is found that the carbonized samples using rice husks (RSH) and apricot seeds (AS) have a porous structure with a specific surface with pore sizes in the nanometer range. The porous structure of the carbonized AS and RSH, and nanometer pore size increases the scattering of light within the absorbing coat and increase the degree of absorption of solar energy. Comparative test of a solar collector with an absorber on the basis of carbonized rice husk with the industrial model of Chinese production has shown its advantage.

409

Study on Self-sinterability of carbon powders manufactured from coal tar for preparation of high density carbon blocks

UISU IM1, Byung-Rok Lee2, Doo-Hwan JUNG1,2,*

[email protected]

1 Advanced Energy Technology, University of Science and Technology University, Daejeon, 305-350, Korea

2 New & Renewable Energy Research Division, Korea Institute of Energy Research, Daejeon, 305-350, Korea

Binderless carbon blocks were prepared from coal tar derived by 2-stage heat treatment.

Carbon materials are widely used for various applications such as the electric, nuclear and chemical industries. In addition, the need to improve the high density has increased due to the increasing demand for high density isotropic graphites in various applications. Generally there are two kinds of method for carbon powder having self-sinterability. The first is mixing the cokes and pitch as filler and binder. But this process is well known that impregnation and baking are repeated to increase the insufficient strength and low density. The second one is to use the mesocarbon microbeads (MCMB) which is able to form itself. The manufacturing cost of MCMB is very high due to several process and yield. In this study, the cokes powder prepared from controlled coal tar by using the 2-stage heat treatment is researched for high density and high strength artifacts.

410

Sunlight-Responsive Photocatalytic Properties of Ag3PO4 Using Graphene Oxide as Template

Yanqing Wang1*, Wei Mao2, Bunshi Fugetsu1, 3, Ichiro Sakata1, 3, Morinobu Endo4,

Mauricio Terrones5 & Mildred Dresselhaus6

[email protected]

1School of Engineering, The University of Tokyo, Bunkyo-ku, Tokyo 113-0032, Japan. 2The Micro Analysis Laboratory, Tandem Accelerator, The University Museum, The

University of Tokyo, 2-11-16 Yayoi, Bunkyo-ku, Tokyo 113-0032, Japan. 3Policy Alternative Research Institute, The University of Tokyo, Bunkyo-ku, Tokyo 113-


Nagano 380-8553, Japan. 5Department of Physics, Department of Chemistry, Department of Materials Science and

Engineering and Center for 2-Dimensional and Layered Materials, The Pennsylvania State University, University Park, PA 16802, USA.

6Research Laboratory of Electronics, Department of Electrical Engineering and Computer Science, Department of Physics, Massachusetts Institute of Technology, 77 Massachusetts

Avenue, Cambridge, MA 02139-4307, USA.

We demonstrate a novel and facile approach for the mass production of tetrahedral Ag3PO4 submicro crystals by using cationic polyelectrolyte poly(diallyldimethylammonium chloride) (PDDA) stabilized graphene oxide (GO) as the functional template. The morphology, size and exposed crystal facets of Ag3PO4 could by tailored by the electrostatically-driven assembly of silver-anion coordination ions on layered GO nanosheets and the orientation growth of Ag3PO4 on GO nanosheets. With further UV irradiation, the aggregation of Ag nanocrystals on Ag3PO4 and the reduction of GO to graphene can be achieved simultaneously in an interactive process. The resulting tetrahedral Ag3PO4-graphene nanosheets (Ag/Ag3PO4/Graphene) composites exhibit higher visible-light-driven photocatalytic activity and structural stability over acridine orange than TiO2 (P25), WO3, and single Ag3PO4 under sunlight irradiation.

411

Superhigh Rate Sodium-Ion Storage Performance of FeSe2/Graphene

Li, D1, Zhou, J1, 2*, Chen, X1 and Song, H1, 2*

[email protected] (Zhou, J), [email protected] (Song, H)


Technology, Beijing 100029, P. R. China. 2Changzhou Institute of Advanced Materials, Beijing University of Chemical Technology,

Jiangsu, P. R. China. Due to the scarcity of lithium resources, abundant, low-cost sodium-ion batteries (SIBs) have attracted more and more attention. However, the low specific capacity and dissatisfactory cycle performance make the sodium-ion battery difficult to realize practical implementation. Therefore, looking for high-performance anode materials is very important for SIBs. In this work, FeSe2 nanorods uniformly anchored on the surface of graphene nanosheets (FeSe2@GNSs) were successfully synthesized by a simple selenization process with Se powders. Our results showed that the FeSe2@GNSs composite exhibits excellent sodium storage properties with a high capacity of 459 mAh/g and a remarkable rate capability simultaneously. The excellent electrochemical properties should be attributed to high purity of FeSe2 as well as rod-like structue, which have higher conductivity and lower phase-transformation resistance, leading to more reversible conversion reaction. This method for design of iron selenide is also expected to be expanded for synthesis of other metal selenide composite materials, and improve their energy storage performance.

412

Surface modification of carbon fibers by electroless tungsten deposition for enhanced electrochemical stability of Lead-Carbon interface

Shu-Huei Hsieh1, Yi-Ren Tzeng2, Ya-Wun Jan3

1Materials Science & Engineering, National Formosa University, Taiwan

2Division of Nuclear Fuels and Materials, Institute of Nuclear Energy Research, Taiwan 3 Innolux Corporation, Taiwan

Energy storage is the key enabling technology for the renewables. The most

convenient method is to use a rechargeable battery to store electric energy in the chemical form. Based on the report by the US national laboratory, Sandia, a new battery design, known as the lead carbon battery, that combines a traditional lead-acid battery with a carbon enhanced supercapacitor electrode in one component has been shown to offer the best potential for economic viability in many energy storage. However, due to the poor wetting of metals on the carbon surfaces, the metal contact of carbon electrode is usually assembled mechanically giving rise to high contact resistance. Under electrochemical conditions, the metal contact on porous carbon electrode is inevitably subjected to interfacial corrosion and eventually the battery will fail.

In this study, we aim to solve the interfacial corrosion problem by forming a chemically stable lead-carbon (Pb-C) interface. We modify the carbon surface by using electroless W plating to study the effect of surface modification on the formation of stable Pb-C bond. Carbon cloth (CC)owns high specific surface areas, complete structure and reliability, although exhibits poor electric-conductivity(~100Ω)，but carbon cloth have been mass-produced in industry. Tungsten carbide is stable, Luthin etc. found that carbon films on tungsten substrates could form small amount of WC at 870 k, therefore if dispersive W nanoparticles deposited on the surface of Carbon fiber, the W will act as an anchor for catching Pb. To do so, we deposit W nanoparticles on the surface of carbon fiber by using the electroless plating. Next, the W/Carbon fiber will also be deposited lead by the electro plating method and heated at the vacuum tube to form chemical bonding at interface.

Fig. 1 and 2 are the SEM photos and EDS analysis of Pb/W/Carbon Fibers composite material after vacuum heat treatment at 600 , which Carbon fibers are electroless W deposited first and then Pb plated. The SEM morphology shown at Fig.1 reveals most Pb particles with 100~200 nm size disperse on the surface of carbon fibers, which confirms that Pb-C has good interface adhesion to inhibit Pb agglomeration. The chemical composition of Pb/W/Carbon Fibers lists at Fig. 2, including Pb and W, the others like Sn, P and Na came from electroless plating, C and O should be Carbon fiber and Oxidation of carbon or lead.

Keywords：electroless W plating, Carbon fiber, lead-carbon (Pb-C) interface

413

Fig 1 SEM photos of Pb/W/Carbon Fiber composite material after vacuum heat

treatment at 600 , which Crabon fibers are electroless W deposited first and then Pb

plated.

Fig 2 EDS analysis of Pb/W/Carbon Fiber composite material after vacuum heat

treatment at 600 , which Crabon fibers are electroless W deposited first and then Pb

plated.

WPb

414

Surface Modification of Porous Carbon and Its Co2 Adsorption Behavior

Chen, S X, Wang, S Y, Liu, F L, Chen S Y


School of Chemistry, Sun Yat-Sen University, Guangzhou, PR China

The CO2 level in the atmosphere has been drastic increasing since two centuries ago. This increase are considered to the mainly reason for global warming, and has drawn widespread attention worldwide. Therefore, the development of efficient methods for CO2

capture with minimal energy penalty has become an increasingly important research subject in both academic and industrial field. Activated carbons receive interest from their excellent adsorption capacity due to their highly porous structures，extended specific surface area, fast adsorption kinetics and easy regeneration. Given all these merits, ACF seems to be a good adsorbent material for carbon dioxide capture. As expected, the adsorption capacities of activated carbons, like those of other physisorbents such as zeolites, decrease rapidly as temperature increases. It is reported that the adsorption capacities dropped from ca. 0.75 to 0.1 mmol/gas the temperature increased from 298 to 373 K. In order to enhance the adsorption capacities, especially at higher temperature, amine was load on to the porous carbon. In this study, surface modification of carbon were investigated, amine loading and its carbon dioxide adsorption behavior was evaluated.

415

Synthesis and Applications of Graphene Quantum Dots

Yichun Yin1, Chenghua Sun2

[email protected]

1School of Chemistry, Monash University, Clayton, VIC 3800, Australia 1,2Department of Chemistry and Biotechnology, Faculty of Science, Engineering and

Technology, Swinburne University of Technology, Hawthorn, VIC 3122, Australia

Graphene quantum dot (GQDs) have been extensively studied due to their unique structures and attractive luminescence properties, but the large-scaled synthesis is an open challenge. In this work, we described an effective technique with the use of molten salts to cut graphene to nano-sized quantum dots with narrowed size-distribution, typically 3-5 nm. In-situ TEM clarified the cutting process, which is essentially driven by the ions released from molten salt based on computational modelling. Such GQDs show excellent luminescence and catalysis performance in the degradation of protein-rich biomass (e.g., hair).

416

Synthesis mechanism of carbon nanotube fiber in the vapor phase

Lee, S-H1, Lee, T1, Lee, H1, Lee J1, Kim, H-R1, Park, J1,2, Lee,K-H1

[email protected]

1Department of Chemical Engineering, POSTECH, Pohang 790-784, Korea 2Carbon Composite Materials Research Center, KIST, Wanju, 565-905, Korea

Carbon nanotube (CNT) fibers, which are collections of many CNTs aligned along the fiber axis, become the global issue as the next generation material with high tensile strength surpassing the carbon fiber. Methods of fabricating CNT fibers may be classified into two categories: Dry-processing (forest and direct spinning) and Wet-processing (solution spinning). In the case of direct spinning, CNT synthesis and fiber fabrication occur simultaneously in a single reactor, so that, it is advantageous in many respects for the mass production of CNT fibers.

However, direct spinning process is difficult to optimize the synthesis conditions, since many variables affect the reaction and the reaction proceeds rapidly at high-temperature. Moreover, understanding about synthesis mechanism is still unclear.

In this work, we optimized the process conditions for the synthesis of CNT fibers using the design of experiments (DOE) technique. DOE is a useful statistical approach for the planning of experimental arrangement and analyzing the results to obtain the most important information with the minimum number of experiments. Furthermore, we proposed the synthesis mechanism based on the decomposition temperatures of materials and verified the hypothesis through the simple modification into the experimental setup. The type of CNTs constituted fibers was changed by controlling the catalyst size. The differences in the products arose from the anti-agglomeration effects of the sulfur atoms. The CNT fiber, which has high IG/ID ratios (69.87), was synthesized from the various feed materials. The knowledges obtained from this work provide useful guides for research on CNT fibers.

417

Synthesis of frost-like CuO combined graphene-TiO2 for high photocatalytic

performance

Dinh Cung Tien Nguyen 1, WooSik Kim 2, Kwang-Youn Cho 2, and Won-Chun Oh 1 *

([email protected])

1 Department of Advanced Materials Science & Engineering, Hanseo University, Seosan, Chungnam, Korea, 356-706

2Korea Institutes of Ceramic Engineering and Technology, Soho-ro, Jinju-Si, Gyeongsangnam-do, Republic of Korea

A novel material, frost-like CuO combined-graphene-TiO2 composite, was successfully synthesized using a self-assembly method. During the reaction, the loading of CuO and TiO2 nanoparticles on graphene sheets was achieved. The obtained CuO-graphene-TiO2 composite photocatalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray (EDX) analysis, transmission electron microscopy (TEM), Raman spectroscopy, ultraviolet-visible diffuse reflectance spectroscopy (UV-vis DRS), and X-ray photoelectron spectroscopy (XPS). The frost-like CuO nanoparticles combined with the small rods TiO2 were successfully loaded on the transparent graphene sheets. The photocatalytic degradation of rhodamine B (RhB), methylene blue trihydrate (MB), and reactive black B (RBB) in an aqueous solution under the visible light irradiation was observed by UV spectrophotometry after measurement of the decrease of their concentrations. The CuO-graphene-TiO2 is expected to become a new potential material for photodegradation activity with excellent photodegradation. Keywords: Graphene nanocomposite, Self-assembly, organic dye photodegradation, Frost-like, CuO.

418

Synthesis of Graphene Based Materials and Fuel Cell Electrocatalyst Applications

Rivera, L.M.1, Montero, C.1, Rodríguez J.L.1, Arévalo, C.1, Lázaro M.J.2, Pastor, E.1

[email protected]

1 Departamento de Química - Instituto de Materiales y Nanotecnología, Universidad de La Laguna, Avda. Astrofísico Francisco Sánchez s/n, 38200 La Laguna, Santa Cruz de

Tenerife, Spain

2 Instituto de Carboquímica (CSIC), C/Miguel Luesma Castan 4, 50018 Zaragoza,Spain

Graphene oxide (GO) is commonly used as a cheap precursor of reduced graphene oxide (rGO), called sometimes “graphene” for their common properties, but strictly it is not the same. GO has low electric conductivity, due to the presence of oxygen groups produced during the synthesis from graphite, which restricts its application in electrochemical devices. To solve this problem a great diversity of physical and chemical methods has been applied for the modification of GO properties, and accordingly, a series of graphenic materials (GMs) have been developed.

For the particular case of Polymer Electrolyte Membrane Fuel Cells (PEMFCs), GMs are often used as catalysts support due to their high conductivity and surface area, or even properly as anode and cathode metal-free catalysts themselves.

In the present work different GMs using GO as precursor were synthesized, which was first obtained by the modified Hummer´s method. GO was reduced following a thermal method and three chemical routes where ethylene glycol, hydrazine and thiourea were used as reducing agents. Then, those materials were used as supports for Pt, Pd and Ni metallic nanoparticles.

GMs were physicochemically characterized by Raman, infrared and X-ray techniques (diffraction (XRD) and energy dispersive (EDX)). The electrochemical performances for the oxygen reduction (ORR), hydrogen evolution (HER) and alcohol oxidation (AOR) reactions were evaluated using several electrochemical techniques as cyclic voltammetry (CV) and the rotating disk electrode (RDE). Results showed that the different routes provided GMs with diverse electrochemistry response, so appropriate design of materials for each reaction can be established.

419

Synthesis of Matrix Graphite Powder For Fuel Element Using Dry Particle Coating

LU Zhen-ming*, ZHANG Jie, ZHOU Xiang-wen, LIU Bing, SHAO Youlin

*Email: [email protected]

Institute of Nuclear and New Energy Technology, Collaborative Innovation Center of Advanced Nuclear Energy Technology, Tsinghua University, Beijing 100084, PR China

The graphite matrix for the HTGR spherical fuel elements are composed by natural

graphite, artificial graphite and resin carbon, which are formed by press of graphite matrix powder, carbonization and purification. So far, the graphite matrix powder is produced by a long wet processing route, including mixing, kneading, granulating, drying and grinding. In this work, composite particles with graphite powder coated by resin is produced by dry particle coating processing. During the processing, the powder is fixed on the inner surface of container by centrifugal force. Due to the compressing and shearing caused by the internal squeezing force, the powder (as host) is coated by resin (as guest), which then spreads and fuses on the surface of powder. According to the experimental results, the electronic conductivity can be effectively used to characterize the resin coating on the powder, and the adjustment of rotor speed and run time controls the coating effect. Besides, the mechanical properties are related to the mixing, coating and sphericity of particles. Therefore, the dry particle coating process is hopeful to replace wet processing because of its simple route, short run-time, high economic efficiency and safety.

420

Synthesis of micro - and nanodiamonds by oxygen-acetylene torch

Medyanova, B1,2, Mansurov, B1, Zhumadilov, B1,2, Partizan, G1,2, Lesbayev B1,2

Presenting author’s e-mail: [email protected] 1 Center of Innovation Technologies at the Institute of Combustion Problems, 050050,

Polezhaeva 20, Almaty, Kazakhstan 2 Al-Farabi Kazakh National University, 050040, al-Farabi ave., 71, Аlmaty,

Kazakhstan

In recent years, nanodiamonds are used in many scientific and technical areas due to unique set of physical, chemical and tribological properties. The simplest but efficient methods for producing carbon materials refers method oxy-acetylene torch, wherein the deposition occurs at atmospheric pressure, i.e. it does not require complex vacuum and electronic equipment. In the course of the studies experiments on synthesis of carbon structures by the method of oxy-acetylene torch on copper films were carried out. Copper films were deposited on substrates of polished silicon plates by DC magnetron sputtering in equipment VUP-5M. The time of experiments was 30 and 60 minutes. A series of experiments in which the distance from the torch nozzle to the substrate (h = 4 mm) and the tilting angle of the flame front (α = 90°) was constant was carried out. The duration of deposition was changed from 15 to 60 minutes, the concentration ratio of oxygen and acetylene (O2/C2H2) was varied from 0.85 to 0.95 in 0.01 increments. According to the analysis by Raman spectroscopy and SEM the obtained samples have a diamond structure with well-defined crystal faces and edges. Analysis of the results of experiments showed that the parameters rendering an important influence on the structure and morphology of the samples are: • The time of deposition of copper film and its thickness, respectively; • The orientation of silicon substrate; • The concentration ratio of oxygen and acetylene. Thus, the process parameters in which occurs the synthesis of micro- and nano-diamonds have been defined.

421

Synthesis of Powders on The Basis of TiB2-TiC By Combustion

Abdulkarimova, R1, Kamunur, K1, Mansurov, Z1,

[email protected]

1Institute of Combustion Problems, Almaty, Kazakhstan

Carbon containing refractory materials are widely used in different fields of engineering and industry due to the combination of their unique properties. At present, self-propagating high temperature synthesis (SHS) allowed to obtain a wide range of such materials. One of the problems in production of carbon containing composition systems is the use of different carbon additives which are able to substitute expensive carbon. The use of a cheap available raw material in production is of great interest. So, at present, utilization of rice husk is an actual problem which is most widely solved by thermal treatment (carbonization). In this study TiB2-TiC containing refractory powders were obtained by SHS from a mixture of TiO2, B2O3 (ore), C (carbonized rice husk - CRH) and Mg. The products SHS were characterized using X-ray diffraction analysis and scanning electron microscopy. The possibility of using borate ore of Inder deposit of the Republic of Kazakhstan for production of boron and carbon containing nanosized refractory powders is shown.

422

Synthesis of SiC nanowires via pyrolysis of silicon-containing carbon materials

Dong, Z1, 2, Meng, J2, Yuan G1, 2, Cong Y1, 2, Zhang J 2, Li X1, 2, 3, Westwood A4


1 The State Key Laboratory of Refractories and Metallurgy, Wuhan University of Science and Technology, Wuhan, Hubei 430081, PR China 2 The Hubei Province Key Laboratory of Coal Conversion & New Carbon Materials, Wuhan University of Science and Technology, Wuhan, Hubei 430081, PR China 3 The research center for advanced carbon materials, Hunan University, Changsha, Hunan 410082, P. R. China 4 School of Chemical and Process Engineering, University of Leeds, Leeds, LS2 9JT, U.K.

SiC nanowires were successfully synthesized without catalyst by pyrolysis of silicon-containing pitch-derived carbon materials in a closed graphite crucible. These silicon-containing carbon materials were obtained by homogenization and co-carbonization of a hybrid precursor consisting of the toluene soluble fraction of coal tar pitch with polycarbosilane. The composition, morphology and structure of the nanowires were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and selected area electron diffraction. The influence of pyrolysis temperature on the growth of the nanowires was investigated by Fourier transform infrared spectroscopy and thermo-gravimetry coupled with mass spectroscopy analysis. The results indicate that the growth of the SiC nanowires starts at around 1200 °C. As the pyrolysis temperature increases to 1300-1500 °C, a large quantity of nanowires are formed on the top surface of the pitch-derived carbon substrate. In addition, increasing the pyrolysis temperature leads to an increase in the average diameter and a change in the typical morphology produced. The synthesized SiC nanowires have single-crystalline structure and are grown along the [111] direction with numerous stacking faults and twins. The vapor-solid mechanism may be responsible for the growth process of the SiC nanowires.

423

The Development of Uranium Absorbent Via Electrochemical Oxidized Graphite Materials

Chen, X T, Lu, Z M, He, L F, Xu, J J, Liu B, Tang, Y P


Institute of Nuclear and New Energy Technology, Collaborative Innovation Center of Advanced Nuclear Energy Technology, Tsinghua University, Beijing 100084, China

During the routine research and production for the fabrication of spherical fuel elements of high temperature gas-cooled reactor (HTGR) in Institute of Nuclear and New Energy Technology of Tsinghua University, a great deal of electrochemical oxidized graphite powder with large specific surface area and abundant oxygen-containing groups is produced. In this study, we prepared a uranium adsorbent functionalized with uranium complex groups on the surface of electrochemical oxidized graphite materials through deep oxidation and chemical grafting. The development of electrochemical oxidized graphite-based uranium absorbent makes the waste profitable, as well as a positive promotion of raw materials closed cycle for nuclear fuel elements production.

424

The effect of parameters on synthesis of carbon nanotube films

Lee, T1, Lee, S-H1, Lee, H1, Lee, K-H1,*

[email protected]

1POSTECH, Pohang, Korea

Floating catalyst method is a kind of chemical vapor deposition (CVD) process. It is referred to the efficient method to synthesize carbon nanotube (CNT) films. However this method is affected by various factors, so it is required to optimize the synthesis condition for high quality CNT films. In general, catalyst precursor, catalyst promotor, carbon source, and carrier gas were injected to the reactor at the same time in this synthesis method. Ferrocene as catalyst precursor and sulfur as catalyst promotor were injected to the reactor in gas phase with the carrier gases (hydrogen and argon). In this work, the studies on the synthesis of high quality CNT films were carried out through the parameter study which changed variables (gas composition, temperature, residence time) affecting the quality of CNT films. The gas composition was changed by controlling the flow rates of hydrogen and methane. The reactor had two furnaces, and they were connected in series. They separated the formation of catalyst particles part and the synthesis of CNT films part. As a result of these experiments, the residence time was the key point among the variables for synthesizing high quality CNT films. The suitable residence time promotes to produce active catalyst, and too long residence time interrupts it. This result is important in synthesizing high quality CNT films. The temperatures profile in the reactor were measured, and the CNT films were analyzed using SEM, Raman spectroscopy to understand the effects of the variables to the quality of CNT films.

425

The Electrochemical Behaviors of Different Types Graphene in Different Electrolytes

Li, XM1, Liu, Z1, Kong, QQ1, Xie, LJ1, Su, FY1, Gao, YD1, Huang, XH1, Guo, XQ1, Zhang, XH1 and Chen, CM1


1 Key Laboratory of Carbon Materials, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, P. R. China.

In this work, two different types of graphene was employed as electrodes. The supercapacitance performance has been investigated and compared at the same graphene to different types of electrolyte and different graphene to the same electrolyte to study. And the heat reduction was applied to obtain graphene with different oxygenic functional groups. Graphene G250 and G1000 worked as the electrodes respectively, which were prepared by chemical methods under 250 (G250 for short) and 1000 (G1000 for short) reduction. 1 M H2SO4, 2 M KOH, 1 M Na2SO4, 2 M NaNO3 and 2 M LiNO3 acted as aqueous electrolytes. To achieve this goal, acidic, alkaline and neutral electrolytes were employed to discuss the match between ionic radius of electrolyte and pore size of electrode, the wettability of electrode in electrolyte and pseudocapacitance reaction of electrode in different electrolytes. The solvated ionic size, wettability of electrolytes and PH of solution are applied to clarify the effect of electrolytes to electrodes. G250 has more oxygen-contained functional groups and the wettability of G250 is better than G1000. Thus, G250 has the highest specific capacitance (208.58 Fg-1) in 2 M KOH, while in 1 M H2SO4 G1000 has the utmost specific capacitance (56.91 Fg-1)Anion show a regulation that the connected resistance between electrode and electrolyte increase in the order of SO4

2->NO3->OH-, which is parallel to the results of EIS analysis.

426

The Influence of Graphene Materials on Silicone Rubber Properties

Sánchez-Hidalgo, R1, Verdejo, R2, López-Manchado, MA2 and Menéndez, R1

[email protected]

1 Instituto Nacional del Carbón, INCAR-CSIC, Oviedo, Spain 2 Instituto de Ciencia y Tecnología de Polímeros, ICTP-CSIC, Madrid, Spain

This study investigates the effect that the addition of graphene materials obtained by thermal reduction of graphene oxide (TRGOs) has on the mechanical, thermal and dielectric properties of silicone rubber composites. Graphene materials were prepared by a modified Hummers method, and then thermally reduced at different temperatures: 400 ºC, 500 ºC, 700 ºC, 1000 ºC and 2000ºC. The dispersion of the graphene material in the rubber matrix was achieved by mechanical mixing in a two-roll mill. The rheological studies performed on the mixtures showed differences in the maximum torque reached depending on the graphene material used. The highest torque was observed in the case of TRGO-700 and TRGO-1000. The highest thermal conductivity was achieved using 5 wt % of TRGO-1000 or TRGO-2000, increasing the initial value up to 45%. This is explained due to a larger sp2 structure restoration compared to other graphene materials. The analysis of the dielectric properties indicated that no percolation occurred except when TRGO-1000 and TRGO-2000 (5 wt %) were used. Differences were also observed in the mechanical behaviour of the silicone rubber depending on the reduction temperature of the graphene material used. The tensile strength decreases with increasing the amount of graphene material used regardless of the type of graphene. The maximum deformation decreases with increasing the amount of graphene in all cases except for TRGO-400, due to the influence of the oxygen functional groups on the vulcanization process. The tensile strength decreases with increasing the amount of oxygen functional groups in the graphene layers.

427

The role of pseudohalides in carbon/carbon electrochemical capacitors

Gorska, B, Bujewska, P, Fic, K



A novel insight into the development of high voltage carbon/carbon electrochemical capacitors operating in aqueous solutions of alkali metals and ammonium thiocyanates (KSCN, NaSCN, LiSCN, and NH4SCN) will be presented.

The effect of salt concentration, electrode porosity and current collectors on the capacitance value, carbon electrode stability, and power performance has been investigated and will be discussed in terms of the activated carbon electrode properties.

Thiocyanate-based electrolytes were selected as cheap and highly conductive electrolytic solutions (up to 401 mS·cm-1 for NH4SCN at 25°C) allowing a cell voltage of 1.6 V in symmetric carbon/carbon system to be reached. At the same time, they displayed an excellent redox activity, enhancing the energy of the device with a good performance during cycling (even up to 100 000 cycles for selected electrolyte formulations and carbon-based electrode compositions).

Moreover, it appeared that the porosity of the carbon electrode played an essential role in energy storage and power delivery processes. Typical microporous carbons with well-developed surface area seem to be not an optimal choice, but carbons with suitable micro-to-meso ratio allow the redox active species to be transported to the interface and then significantly improves both energy and response time. Furthermore, the stability of the carbon electrode as well as SCN- against oxidation has been confirmed by Raman in-situ technique; no remarkable changes during several scans indicates excellent stability of the system.

428

The Structure and properties of carbon microspheres with double shells

Mei Niu1,3, Baoxia Xue1,2,3, Yongzhen Yang1,2, Jie Bai3, Yinghao Song3, Yun Peng3, Xuguang

Liu1,4


1Key Laboratory of Interface Science and Engineering in Advanced Materials, Taiyuan University of Technology, Ministry of Education, Taiyuan,China

2Research Center on Advanced Materials Science and Technology, Taiyuan University of Technology, Taiyuan, China

3College of Textile Engineering, Taiyuan University of Technology, Yuci 030600, China 4College of Chemistry and Chemical Engineering, Taiyuan University of Technology,

Taiyuan, China

Carbon microspheres (CMSs) as core materials had been coated by two capsular walls with magnesium hydroxide (MH) as the first inorganic layer and poly (ethylene terephthalate) (PET) as the second organic layer. MH coating CMSs (MCMSs) were obtained by liquid phase deposition method. And MCMSs with PET modification (PMCMSs) were prepared through in situ polymerization method. Morphologies, structures and dispersions of PMCMSs have been studied by FESEM, TEM,FTIR and XRD. The results showed that MH and PET as two capsular walls were coated on the surface of CMSs with the optimal thickness of about 70nm.The PMCMSs owned better dispersion in PET matrix. A series of PET blends were prepared by direct melt compounding with PMCMSs as flame retardant. Compared with MCMSs/PET composites, the mechanical properties of PMCMSs/PET composites had significantly increased because of good dispersion and the strong interface binding force between PMCMSs and PET matrix. Moreover, PMCMSs was proved to be an effective flame retardant. For PMCMSs/PET with 2 wt% PMCMSs, the LOI value increased from 21.0% of pristine PET to 27.2%, and the pk-HRR value decreased from 513.22KW/m2 of pristine PET to 352.14 KW/m2. The decreased SPR and TSP values demonstrated PMCMSs suppressed the smoke production. Moreover, the increased FPI value illustrated that PMCMSs reduced the fire risk of PET significantly. Overall, PMCMSs/PET composites have good mechanical and flame-retardant properties because of two capsular walls on the surface of CMSs.

429

Thermodynamic Calculations of Initial Steps In Methane Pyrolysis

Hu, C1, Li, H1, Zhang, S1



Methane pyrolysis is still partly understood, although it is often proposed as a useful method for carbon deposition. In this work, thermodynamic analysis of the initial steps in methane pyrolysis was carried out with quantum chemical method realized in Gaussian software. The method of the calculation is density functional theory and the theoretical approximation is B3LYP model with 6-31G basis. The reactions involved were the initial steps in methane pyrolysis with ethylene as the main impurity in methane. We have shown that the chosen method is applicable for the calculations. The thermal energy, enthalpy, entropy, and Gibbs free energy of the reactions are presented in a wide range of temperatures and pressures. Most reactions are endothermic and have lower Gibbs free energies at high temperatures. For thermodynamic properties of the reactions, temperature is more important than pressure. The results of this work could be used to explain the beginning stage of methane pyrolysis and to develop a kinetic model for the whole process.

430

Thermophysical properties of carbon fibre reinforced multilayered (PyC-SiC)n matrix composites

Yan Jia 1, Kezhi Li 1


1 Northwestern Polytechnical University, Xi’an, Shaanxi, P.R. China

Three kinds of carbon fibre reinforced multilayered (PyC-SiC)n matrix (C/(PyC-SiC)n) composites with (PyC–SiC)1, (PyC–SiC)2 and (PyC–SiC)4 matrices were prepared by means of layer-by-layer deposition of PyC and SiC via isothermal chemical vapour infiltration. Thermal expansion behaviours in the temperature range of 800-2500 ºC and thermal conductivity from room temperature to 1900 ºC of C/(PyC-SiC)n composites with various microstructures were investigated. The results show that with increasing the number of sequences (n), coefficients of thermal expansion (CTEs) and thermal conductivity decrease due to the increase of interfaces. CTEs of the composites measured in both parallel (XY) and perpendicular (Z) to non-woven carbon cloth directions decrease gently from 800 to 1200 ºC and then decrease sharply reaching the minimums at around 1500 ºC. Above 1500 ºC, CTEs in XY direction increase as temperature increases. On the contrary, CTEs in Z direction increase to the peak values at about 1800 ºC and fall rapidly to valley values at about 2100 ºC, then again increase linearly until 2500 ºC. CTEs vary from 1 to 4.5 10-6 /K and from 3.7 to 6.5 10-6 /K in XY and Z directions, respectively. Thermal conductivity measured in Z direction increases with the increase of temperature for the three composites, ranging from 5.1 to 20.6 W/m K. A model is developed to estimate the thermal conductivity based on the weight fraction of ingredients and open porosity of the composites. The theoretical values are found to be in accordance with the experimental values.

431

TiCo/Graphene based nanocomposites and its activity towards oxygen reduction reaction.

Luque-Centeno, J. M.1, Martínez-Huerta, M.V.2, Lemes, G.1, Pastor, E.3, Lázaro, M.J.1.


1Instituto de Carboquímica (CSIC), Miguel Luesma Castán 4, 50018 Zaragoza, Spain. 2Instituto de Catálisis y Petroleoquímica (CSIC), Marie Curie 2, 28049 Madrid, Spain.

3Universidad de La Laguna, Instituto de Materiales y Nanotecnología, Dpto. Química-UD Química-Física, Avda. Astrofísico Francisco Sánchez s/n, 38206 La Laguna (Tenerife),

Spain.

The use of electrochemical devices like fuel cells (FC) for electric energy production is considered to be a promising option toward energy and environmental problems. Actually, FC works on acidic media, but with some limitations like high cost of production and degradation by the use of precious metals like platinum. Alkaline FC appears as a good alternative. Alkaline media avoids the corrosion problems and increase the kinetic reaction process. This makes possible the use of non-precious metals as catalysts. The high activity of catalysts based on cobalt toward oxygen reduction reaction (ORR) has been reported in several articles. In addition, the use of titanium and its derivatives like nitrides and carbides had demonstrate good properties for decrease the metal charge and increase the stability of catalysts. The aim of this work is the use of cobalt and titanium as non-precious metals for ORR catalysts. As support, graphene oxide has been employed due to its great properties like high resistance and electrical conductivity. Sol-gel method has been applied for the synthesis of graphene/Ti/Co composites, which have been calcinated at different temperatures and treatment times. These composites have been structurally characterised by elemental analysis, ICP-MS, X-ray diffraction spectroscopy (XRD), Transmission Electron Microscopy (TEM), Raman Spectroscopy and X-ray Photoelectron Spectroscopy (XPS). The electrocatalytic activity towards the ORR has been measured with a three-electrode system in alkaline media, using a glassy carbon in a rotatory disk electrode (RDE) supporting the catalyst ink as working electrode.

432

Topological Defects in Metal-Free Nanocarbons For Oxygen Electrocatalysis

Qiang Zhang1,*



Heteroatom-doped nanocarbons are considered promising metal-free catalysts for both oxygen reduction and oxygen evolution reactions. However, the origin of electrocatalytic activity in such materials is normally based on a trial and error approach and therefore remains unclear. Herein, a bifunctional graphene catalyst containing nitrogen heteroatom dopants and edge-rich defects as active sites was proposed to probe the underlying mechanism behind the electrocatalytic activity. This ubiquitous graphene material with abundant topological defects is achieved via the carbonization of natural gelatinized sticky rice on hard templates and afford superb bifunctional oxygen electrocatalysis performance. The first-principle simulations reveal the critical importance of edge and topological defects in the activity originate of metal-free nanocarbons for oxygen electrocatalysis. A nitrogen-free configuration with adjacent pentagon and heptagon carbon rings exhibits the lowest overpotential with 0.14 V for ORR and 0.21 V for OER. The synthetic strategy and insights on the ORR and OER mechanism facilitate the development of advanced metal-free carbocatalysts for a wide range of electrocatalytic applications.

References

13) Tang C, Wang HF, Chen X, et al. Adv Mater 2016, 28, 6845.

14) Tang C, Zhang Q. Adv Mater 2017. 29, 1604103.

433

Treatment of Capsule Carbon Nanomaterials With Nitrogen Plasma Irradiation

Takahashi, R1, Harigai, T1, Takikawa, H1, Suda, Y1


1 Toyohashi University of Technology, Toyohashi, Japan

Doping a carbon nanomaterial with other atomic species including nitrogen provides a means of altering its electronic and transport properties. Carbon nanoballoons (CNBs) have a pentagonal ring in a part of a graphitic layer with hexagonal rings. CNBs have a hollow structure with high conductivity. To control their electronic property, we performed a substitutional doping of nitrogen atoms by using nitrogen radio-frequency plasma. CNBs were synthesized by a heat treatment of a particulate carbon nanomaterial at 2600 degree Celsius in argon gas. CNBs mixed with polyvinylidene difluoride in a mass ratio of 9:1 was applied to a silicon substrate and dried. Nitrogen radio-frequency magnetron plasma was applied to CNBs. X-ray photoelectron spectroscopy was used to determine the chemical bonding of the treated CNBs.

434

Tumor-Targeting Fullerenol Epri-Fluorescence Imaging Probe

Pan Y, Shen Y, Liu F, Chen S, Yan, G*


School of Material Science and Engineering, Wuhan Institute of Technology, Wuhan 430074, China

Electron paramagnetic resonance imaging (EPRI) and fluorescent imaging (FI) are the rapidly growing imaging modalities for detecting the tumors in the clinical research. The ideal agents, such as EPRI probe and FI probe, will be designed as the tumor-targeting pharmaceuticals with high imaging contrast enhancement and low toxicity. Glypican 3 (GPC3) is preferentially expressed in the majority of hepatocellular carcinoma (HCC) tissues. An anti-Glypican-3 monoclonal antibody (GPC3-mAb) can induce the great sensitivity and specificity against GPC3, which may be of value for the early diagnosis of HCC in an antigen-dependent manner. Fullerenol is a promising nanomaterial because of its negligible toxicity and high radical scavenging ability and then chosen as a water-soluble carrier. A fullerenol derivative was synthesized by the incorporation of GPC3-mAb, 5-formyl-1,1,3,3-tetramethyl-isoindolin-2-yloxyl (FTMIO) and naphthalimide (NI) into fullerenol C60(OH)11. The Fullerenol derivative was further characterized and its property was also evaluated. The derivative had similar electrochemical and redox property as TMIO and similar fluorescent property as NI. Moreover, the derivative possessed low cytotoxicity to HeLa cells and high specific uptake by HepG2 tumor cells, and then displayed strong green fluorescence imaging in the HepG2 cells excited by the blue light. This derivative can disperse homogeneously in aqueous solution and be used as a potential tumor-targeting nano EPRI-NI imaging probe. This work was supported by the National Natural Science Foundation of China (Grant No. 51373128), Key National Research and Development Program (2016YFB1101302), and Wuhan Science and Technology Innovation Team of Hi-tech Industrial Project, Hubei Province (Grant No. 2015070504020217), China.

435

Tuning fluorine and oxygen distribution in graphite oxifluorides

Mar, M1,2,3, Dubois, M1,2, Guérin, M1,2, Batisse, N1,2, Simon, B3, Bernard, P3


1Clermont Université, Université Blaise Pascal, Institut de Chimie de Clermont-Ferrand, BP 10448, F-63000 Clermont-Ferrand, France

2CNRS, UMR 6296, Institut de Chimie de Clermont-Ferrand, F-63171Aubière, France 3SAFT, Direction de la recherche, 111-113 Bd A. Daney, F-33074 Bordeaux, France

. Fluorine Graphite intercalation compounds (F-GICs) have been widely studied for their electrochemical applications especially in primary lithium batteries. Nevertheless, higher capacity is reached for oxygen-GICs (above 990 mAh/g versus 865 mAh/g for F-GICs). Oxifluorides offer then versatility to design cathode materials delivering the upmost performances. Combine to choice of the precursor (either graphite oxide or sub-fluorinated graphite fluoride, two-step synthesis processes, which include Hummers’ oxidation and direct fluorination, allow the tuning of the fluorine and oxygen atoms distribution. According to the sequence, i.e. fluorination/oxidation or oxidation/fluorination, several oxifluorides were then prepared and appeared suitable for the application. In the one hand, direct fluorination using F2 gas resulted in homogeneous fluorine dispersion when precursor was graphite oxide. In the other hand, Hummers’ oxidation, safer and quicker path, was modulated according to the temperature parameter. Different oxygen contents, as well as different functional compositions were obtained. Characterization of the final objects was achieved thanks to cross-checked data. Main chemical data came from multinuclear solid-state MAS-NMR which provided information on atomic and functional compositions. C-OH, C-O-C, COOH, F(C=O), CF, CF2 and CF3 were identified. Moreover covalence and environment, especially in-plane organization of the fluorine and oxygen containing groups, were assessed. Out-plane organization was emphasized by polyphasic objects with radial geometry.

436

Unphysical nucleation of diamond in the extended cutoff Tersoff potential

Aghajamali, A1, de Tomas, C1, Suarez-Martinez, I1, Marks, NA1



Molecular Dynamics simulations of carbon materials is a challenging problem. This is mainly due to the difficulties in constructing an interatomic potential that represent carbon’s complexity of the competing hybridizations as well as long-range effects associated with -electrons. More than 40 carbon potentials and modifications have been published but their transferability across different situations is not always appropriate [1]. The first useful potential for carbon only appeared in 1988 from Tersoff [2] and since then a number of modifications and reparametizations have been published in order to correct some its deficencies. Here we reveal an up-to-now unknown deficiency of the Tersoff potential associated with modification of its cut-off radius. We show that the common modification known as ‘extended Tersoff’ expands the cutoff of the potential into the second neighbour coordination shell, resulting in the unphysical nucleation of diamond during annealing of amorphous carbon. [1] de Tomas, C., Suarez Martinez, I., & Marks, N. A. (2016). Carbon, 109, 681-693. [2] Tersoff, J. (1988). Physical Review Letters, 61, 2879-2882.

437

Self-healing YSZ-La-Mo-Si heterogeneous coating fabricated by plasma spraying to protect carbon/carbon composites from oxidation

Wang, C.C.1, Li, K.Z.1, Shi, X.H.1,

Author’s e-mail: [email protected], [email protected], [email protected];


To protect carbon/carbon (C/C) composites against oxidation, YSZ-La-Mo-Si (YSZ-LMS) heterogeneous coating was prepared by the plasma spraying using YSZ (Y2O3-stabilized ZrO2), MoSi2 and LaB6 as raw materials. The thermogravimetric and isothermal oxidation results indicated that the as-prepared coating reveal superior oxidation protective ability at elevated temperatures, which protected the C/C composites from oxidation for 50 h at 1773 K with a mass loss of 0.58 % (1.31 mg·cm-2). The generation of SiO2, ZrSiO4, Y2SiO5 and La2O3 expanded the volume of solid phase and decreased the volatilization of SiO2 to form a denser Zr-Y-La-Si-O oxide glass layer. Among them, the volume expansion promoted the formation of compressive stress within the coating at this high temperature. These compressive stresses restrain the initiation and propagation of cracks and boost the oxidation protection of the coating for C/C composites. The corresponding high temperature oxidation activation energy of the coated C/C composites at 1573-1773 K is calculated to be 74.466 kJ/mol.

[i] G-P. Hao, G. Mondin, Z. Zheng, T. Tiemelt, S. Klosz, R. Schubel, A. Eychmüller, S. Kaskel. Angew. Chem. Int. Ed., 2015, 54, 1941–1945. [ii] G-P. Hao, N. R. Sahraie, Q. Zhang, S. Krause, M. Oschatz, A. Bachmatiuk, P. Strasser, S. Kaskel, Chem. Commun., 2015, 51, 17285–17288. [iii] G-P. Hao, Q. Zhang, M. Sin, F. Hippauf, L. Borchardt, E. Brunner, S. Kaskel, Chem. Mater., 2016, 28, 8715–8725.

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