nirh nanoparticles supported on nitrogen-doped porous

Nano Res

1

NiRh nanoparticles supported on nitrogen-doped

porous carbon as highly efficient catalysts for

dehydrogenation of hydrazine in alkaline solution

Bingquan Xia1, Kang Chen1, Wei Luo1,2 (), and Gongzhen Cheng1

Nano Res., Just Accepted Manuscript • DOI 10.1007/s12274-015-0845-4

http://www.thenanoresearch.com on June 23, 2015

© Tsinghua University Press 2015

Just Accepted

This is a “Just Accepted” manuscript, which has been examined by the peer-review process and has been

accepted for publication. A “Just Accepted” manuscript is published online shortly after its acceptance,

which is prior to technical editing and formatting and author proofing. Tsinghua University Press (TUP)

provides “Just Accepted” as an optional and free service which allows authors to make their results available

to the research community as soon as possible after acceptance. After a manuscript has been technically

edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP

article. Please note that technical editing may introduce minor changes to the manuscript text and/or

graphics which may affect the content, and all legal disclaimers that apply to the journal pertain. In no event

shall TUP be held responsible for errors or consequences arising from the use of any information contained

in these “Just Accepted” manuscripts. To cite this manuscript please use its Digital Object Identifier (DOI®),

which is identical for all formats of publication.

Nano Research

DOI 10.1007/s12274-015-0845-4




Bingquan Xia1, Kang Chen1, Wei Luo1,2*, Gongzhen

Cheng1

1 Wuhan University, China; 2 Suzhou Institute of Wuhan

University, China

Nitrogen-doped porous carbon (NPC) derived from metal-organic

frameworks (ZIF-8) have been utilized to support bimetallic NiRh

nanoparticles (NPs) as efficient catalyst toward hydrogen generation

from hydrazine. The NiRh NPs supported on NPC derived from

carbonized ZIF-8 at 900 °C exhibit the highest catalytic activity and

100% hydrogen selectivity.




Bingquan Xia1, Kang Chen1, Wei Luo1,2(), and Gongzhen Cheng1

Received: day month year

Revised: day month year

Accepted: day month year

(automatically inserted by

the publisher)

© Tsinghua University Press

and Springer-Verlag Berlin

Heidelberg 2014

KEYWORDS

Hydrogen storage; MOFs;

nitrogen-doped porous

carbon, hydrazine

ABSTRACT

Well dispersed bimetallic NiRh nanoparticles (NPs) with different compositions

supported on nitrogen-doped porous carbon (NPC) derived from metal-organic

frameworks (ZIF-8) have been synthesized through a co-reduction method.

NPCs derived from ZIF-8 carbonized at 800 °C, 900 °C and 1000 °C are denoted

as NPC-800, NPC-900 and NPC-1000, respectively. Compared with NPC-800,

NPC-1000, and other commercial supported materials, the NPC-900 supported

NiRh catalyst exhibits the highest catalytic activity and 100% hydrogen

selectivity toward hydrogen generation from hydrazine. These properties might

be attributed to the high surface area and high graphitization of NPC-900. This

strategy may open up a new avenue for designing high-performance catalysts

by utilizing NPC as a support to anchor active metal NPs for more applications.

1 Introduction

Safe and effective storage of hydrogen is still one of

the most challenging obstacles in the widespread

application of hydrogen fuel cells [1, 2]. In recent

years, numerous condensed-phase hydrogen storage

approaches in which large quantities of hydrogen

stored at a low pressure have been widely explored,

including physical sorbent materials[3], and chemical

hydride systems [4-8]. Among them, hydrous

hydrazine have been extensively investigated as a

promising liquid-phase chemical hydrogen storage

material, due to its high content of hydrogen (8.0

wt%), easy recharging ability, and environmental

friendliness (nitrogen is the only by-product via a

complete decomposition way (Eq. (1)) [9]. However,

from the perspective of hydrogen storage application,

the undesired incomplete reaction pathway

producing ammonia (Eq. (2)) should be avoided. To

date, a number of noble metal nanocatalysts have

Nano Research

DOI (automatically inserted by the publisher)

Address correspondence to [email protected]

Research Article

| www.editorialmanager.com/nare/default.asp

2 Nano Res.

been developed. However, the key objective is still

finding a balance between the cost, selectivity,

efficiency and recyclability [10]. To overcome the

problem, the introduction of non-noble metals into

the catalysts for the efficient decomposition of

hydrous hydrazine has gained increasing research

interests [11-14]. To this end, numerous materials

have been developed to disperse active metal NPs

without aggregation and facilitate the electron

transfer and mass transport kinetics during the

catalytic reaction [15, 16].

Graphitic carbons with high degree of

graphitization have abundant free-flowing π

electrons, would favor the dispersion of metal NPs

and the transfer of electrons. When doped with

nitrogen, the carbon π electrons can be activated by

conjugating with the lone-pair electrons from N

dopants to generate a net positive charge on

neighboring carbon atoms in the carbon plane,

which could attract electrons and thus facilitate the

catalytic activity [17]. Due to the diverse

composition, ultrahigh surface area, and ordered

porous structure, metal-organic frameworks (MOFs)

have been studied as precursors to make highly

porous carbon materials under thermolysis

conditions [18, 19]. Among them, the zeolitic

imidazolate framework (ZIF-8) with a high carbon

content and nitrogen-containing ligand is a good

candidate to make nitrogen-doped porous carbon

(NPC) by direct carbonization [20]. NPC derived

from MOFs has been widely studied in clean energy

application, such as gas storage and separation [21],

lithium-ion batteries [22, 23], supercapacitors [24,

25], solar cells [26], oxygen reduction electro-

catalysts [27, 28], and so on. However, direct growth

and anchoring active metal NPs on NPC derived

from MOFs with enhanced catalytic activity has

been rarely reported.

Herein, for the first time, NiRh NPs with different

compositions have been successfully immobilized

on the NPC derived from ZIF-8 by a simple

co-reducing method. Among all the catalysts tested,

Ni3Rh7/NPC-900 exhibits the highest catalytic

activity with turnover frequency (TOF) value of 156

h-1, and 100% hydrogen selectivity toward

hydrogen generation from hydrazine in alkaline

solution at 50 °C.

2 Experimental

2.1 Synthesis of ZIF-8 derived nitrogen-doped

carbon

The preparation of ZIF-8 derived nitrogen-doped

carbon involves hydrothermal synthesis and

carbonization of ZIF-8. ZIF-8 was synthesized

according to the reported procedure (for more

details in ESM) [29]. The thermal calcination

procedures of ZIF-8 samples were applied under Ar

flow at target temperature (800, 900 and 1000 °C)

with a heating rate of 5 °C/ min. After reaching the

target temperatures，it was kept constant for 6 h and

then cooled down to room temperature naturally.

The carbonized ZIF-8 samples were immersed in

HCl solution under magnetic stirring for 24 h to

remove the Zn species. The black precipitates were

collected by centrifugation, and washed with water

and ethanol, then dried under vacuum conditions

for 24 h at room temperature. The obtained samples

were designated as “NPC-n”, where the “n”

indicates the calcination temperature.

2.2 In situ synthesis of NiRh/NPC-n catalysts and

hydrogen generation tests

Typically, 10 mg carbonized ZIF-8 samples

(NPC-900) were well dispersed in 5 mL aqueous

solution containing 0.01 mmol RhCl3·3H2O and 0.09

mmol NiCl2·6H2O kept in a two-necked

round-bottom flask by sonication. The resulting

mixture was then reduced by 5 mL mixed solution

of 37.8 mg NaBH4 and 200 mg NaOH with vigorous

stirring at 25 °C. One neck was connected to a gas

burette to monitor the volume of the released gas,

www.theNanoResearch.com∣www.Springer.com/journal/12274 | Nano Research

3 Nano Res.

and the other neck was used to introduce hydrazine

monohydrate (0.1 mL, 1.96 mmol). The temperature

of the reaction solution was controlled at 323 K

through water bath. The gas released during the

reaction was passed through a HCl solution (1.0 M)

before being measured volumetrically. The

selectivity towards H2 generation (X) can be

calculated using equation below.

3 Results and discussion

As illustrated in Scheme 1, the preparation of

carbonized ZIF-8 involves a facile hydrothermal

synthesis of ZIF-8 at low temperature, followed by

carbonized at high temperature under argon

atmosphere (Fig. S1). The obtained materials were

designated as NPC-n, where n stands for the

annealing temperature. ZIF-8 was synthesized

according to the reported procedure [29], which is

similar to the stimulated ZIF-8 from powder X-ray

diffraction patterns (PXRD) (Fig. 1(a)). After

carbonization at high temperature, the result black

powder samples were soaked in HCl solution to

remove the residual Zn species. The degree of

graphitization and the amount of N dopant is

closely associated with temperature, while the

graphitization of carbon needs high temperature,

and the high temperature leads to the loss of

nitrogen. In order to control the N/C ratio and

degree of graphitization in the carbonization, these

ZIF-8 samples were annealed at different

temperatures at 800, 900 and 1000 °C.

Scheme 1 Illustration of the preparation of ZIF-8 derived

nitrogen-doped carbon.

10 20 30 40 50 60

Inte

ns

ity

(a

.u.)

2 Theta (degree)

NPC-800

NPC-900

NPC-1000

(002)

(101)

10 20 30 40 50

Inte

ns

ity

(a

. u

.)

2 Theta (degree)

As-prepared

Simulated

Figure 1 Powder XRD patterns of ZIF-8 before (a) and after (b)

carbonization.

The PXRD patterns of three samples display two

broad peaks at around 25° and 44° (Fig. 1(b)),

corresponding to the amorphous carbon (002) and

graphitic carbon (101) diffractions, respectively [20,

27]. The peak of NPC-1000 at 44° is most intensive,

followed by NPC-900 and NPC-800, indicating the

high temperature leads to the graphitic structure of

carbon materials [20]. No diffraction peaks of Zn

impurities were observed in the ZIF-8 derived

carbons，indicating that the residual carbon reduced

Zn metal was removed by vaporization away along

with the Ar flowing and leached by acid treatment

[30]. The N2 adsorption desorption isotherms of

NPC-800, NPC-900 and NPC-1000 are shown in Fig.

S2 in the Electronic Supplementary Material (ESM),

and the BET surface areas of NPC-800, NPC-900

and NPC-1000 are 1864.0, 1996.1 and 1713 .9 m2/g,

further confirming the highly porous structure of

NPCs (Table S1).

406 404 402 400 398 396

Inte

ns

ity

(a

.u.)

Binding Energy (eV)

NPC-800

NPC-900

NPC-1000

N1N2N3

0

20

40

60

80

100

Pe

rce

nta

ge

(%

)

C

O

N

NPC-800 NPC-900 NPC-1000

8.153.71 2.45

Samples

900 800 700 600 500 400 300 200 100 0

Inte

ns

ity

(a

.u.)

Binding Energy (eV)

NPC-800

NPC-900

NPC-1000O1s

N1s C

1s

294 292 290 288 286 284 282

Binding Energy (eV)

NPC-800

C1

Inte

ns

ity

(a

.u.)

NPC-900

NPC-1000

C3 C2

Figure 2 (a) XPS spectra and (b) High-resolution C1s spectra and (c) High-resolution N1s spectra for NPC-800, NPC-900 and

NPC-1000 (c) Atomic percentage of carbon, oxygen and nitrogen in NPCs obtained from XPS spectra, (d) nitrogen-doped carbon

structure. (N1, N2 and N3 correspond to pyridinic N, pyrrolic N and graphitic N).

Raman spectroscopy which provides structural

information on different forms of carbon, such as

the defects, the ordered structures, and the

grapheme layers, has been widely utilized to

characterize the textural quality of carbon based

materials [31]. The Raman spectra of NPCs exhibit

two remarkable peaks at around 1350 and 1580 cm-1

(Fig. S3), corresponding to the well-defined D band

and G band, respectively [32]. As we know, the D

band in Raman spectra is closely associated with

structural defects and partially disordered

structures of the sp2 domains, while the G band

related to the E2g vibration mode of sp2 carbon

domains could explain the graphitization degree

[33]. The D band in NPC-800 is more intensive than

NPC-900 and NPC-1000, and the ID/IG values of

NPCs decrease from 0.93 to 0.89 due to different

carbonization temperature. Those indicate that

partial sp2 domains were restored at different levels,

and the graphitic degrees of NPC samples were also

improved accordingly due to the reduction effect

and “self-repairing” of the graphene layer at high

temperature [32].

In order to analyze the elemental composition

and nitrogen bonding configurations in NPCs,

X-ray photoelectron spectroscopy (XPS) charac-

terizations were further applied. The XPS spectrum

of the ZIF-8 derived NPCs distinctly shows the

presence of carbon, oxygen and nitrogen atoms in

Fig. 2a. The peaks of NPC samples at approximately

400.0 eV in the spectra were attributed to the

nitrogen species, clarifying the incorporation of

nitrogen atoms within the carbon networks. The

C1s peaks for the NPCs were centered at

approximately 285.0 eV, which is characteristic for

nitrogen-doped carbon adsorbed materials [17]. The

presence of oxygen can be attributed to moisture,

atmospheric O2 or CO2 on ZIF-derived carbon as

well as the residual oxygen containing groups from

ZIF-8 [27]. The percentages of doped N content of

NPCs estimated from the XPS spectrum were

8.15 atomic%, 3.71 atomic%, and 2.45 atomic%.


5 Nano Res.

The high content of nitrogen in NPC-800 may be

explained by the incomplete pyrolysis of organic

linkers during the calcination process [34]. Rising

the annealing temperature from 800 to 1000 °C

(Fig. 2b), may result in the cleavage of C–N and

release of nitrogen. It is likely that the C-N bonds

were partially destroyed during the

graphitization process in ZIF-8, leading to the

lower N content in the NPC-900 and NPC-1000

samples [32]. It can be revealed from the high

resolution C1s spectra (Fig. 2b) that the dominated

peaks positioned at 284.8 eV is attributed to

graphitic sp2 carbon(C=C), while the peaks at 285.5

± 0.2 eV and 287. 7± 0.2 eV ascribe to C=O/C-N and

C=N/C-O [27, 32]. The bonding configurations of

nitrogen atoms in NPCs were further characterized

by high-resolution N1s spectra. The N1s spectra of

NPC can be fitted into three peaks at 398.2, 399.5,

401.1 eV (Fig. 2c). The peaks with lower binding

energy located at about 398.2 and 399.5 eV,

respectively, correspond to pyridinic-N and

pyrrolic-N [17, 35], as illustrated in Fig. 2d, which

contribute to the π-conjugated system with a pair of

p-electrons in the graphene layers. When carbon

atoms within the graphene layers are substituted by

nitrogen atoms in the form of “graphitic” nitrogen,

the corresponding peak in the high-resolution N1s

spectra is located at 400.8-401.2 eV [35]. It is also

found that increasing the annealing temperature

results in more graphitic N incorporated into the

carbon networks. These results indicate that

pyridinic nitrogen and graphitic nitrogen are the

main nitrogen component in our prepared NPCs

(Fig. 2c and Table S2).

The bimetallic NiRh NPs with different

compositions were immobilized on NPC-900, and

tested for the catalytic activity toward the

dehydrogenation of hydrazine in the presence of

NaOH (0.5 M) at 50 °C. The compositions of NiRh

catalysts were further checked by inductively

coupled plasma-atomic emission spectroscopy

(ICP-AES), which were identical to the ratios of

Table 1 Comparison of the TOF values of different

catalysts for dehydrogenation from N2H4·H2O in

aqueous solution.

Catalyst T/ K TOF/ h-1 Reference

NiRh4 298 12 [36]

NiRh4/graphene 298 25.0 [37]

Ni90Rh10 323 4.5 [38]

Ni66Rh34@ZIF-8 323 104 [39]

Ni3Rh7/NPC-900 323 156 This work

Ni0.6Pd0.4 323 75 [40]

Ni0.99Pt0.01 323 36 [41]

NiPt0.057/Al2O3 303 16.5 [42]

Ni80Pt20@ZIF-8 323 90 [43]

Ni0.9Pt0.1/Ce2O3 298 28.1 [44]

Ni0.95Ir0.05 298 4.5 [45]

Ni/Al2O3 303 2.2 [42]

[a] TOFinitial was calculated when the conversion reached 50%.

their metal precursors. As shown in Fig. 3, the

hydrogen selectivity and catalytic activity were

strongly dependent on the ratio of Ni/Rh.

Ni/NCP-900 was almost inactive, and the catalytic

activity and hydrogen selectivity were increased by

alloying Rh to Ni, while Ni3Rh7/NPC-900 exhibits

the highest catalytic activity, with the turnover

frequency (TOF) value of 156 h-1 at 50 °C, which is

higher than most of the reported values (Table 1).

Further increasing the amount of Rh results in the

decrease of catalytic activity and hydrogen

selectivity, highlighting the synergistic effect of

molecular-scale Ni-Rh alloying compositions in

NPC-900 for their catalytic activity. The H2

selectivity and completeness of hydrazine

decomposition over Ni3Rh7/NPC-900 are further

confirmed by mass spectroscopy (Fig. S4),

indicating the 100% H2 selectivity. In addition, the

catalytic activity of Ni3Rh7 supported on NPC

carbonized at different temperature were also

investigated. The catalytic performance of

Ni3Rh7/NPC-900 is superior to those of

Ni3Rh7/NPC-800 and Ni3Rh7/NPC-1000 (Fig. S5),

which may be supported on NPC carbonized at

0 10 20 30 40 50 60

0

1

2

3

Ni

Ni9Rh

1

Ni7Rh

3

Ni5Rh

5

Ni3Rh

7

Ni1Rh

9

Rh

n(N

2+

H2)/

n(N

2H

4)

t (min)

0

20

40

60

80

100

120

140

160

TO

F (h

-1)

Ni

Rh 1

Ni 9

Rh 3

Ni 7

Rh 5

Ni 5

Rh 7

Ni 3

Rh 9

Ni 1

Rh

0

20

40

60

80

100

H2 selectivity

TOF

Pe

rce

nta

ge

(%

)

Figure 3 (a) Time course plots and (b) corresponding H2 selectivity and TOF values for the decomposition of hydrazine over

different NiRh/NPC-900 with NaOH (0.5 M) at 50 °C. (metal/N2H4•H2O = 0.05)

different temperature were also investigated. The

catalytic performance of Ni3Rh7/NPC-900 is

superior to those of Ni3Rh7/NPC-800 and

Ni3Rh7/NPC-1000 (Fig. S5), which may be caused by

the high surface area and high graphitization of

NPC-900. These are also the significant factors in

catalytic electrochemical oxygen reduction reactions

[27, 46]. In NPC-n, the effective incorporation of

pyridinic nitrogen would generate defects, and thus

activate the carbon network. Moreover, the high

surface area for adsorption of N2H3 would also

facilitate their catalytic activities.

Additionally, to investigate the effects of the

supported materials on the catalytic activities

performances thoroughly, the as-synthesized

Ni3Rh7 catalysts, Ni3Rh7/NPC-900, Ni3Rh7/-Al2O3,

Ni3Rh7/SiO2, Ni3Rh7/C and Ni3Rh7/PVP are prepared

and their catalytic performances on hydrogen

generation from aqueous solution of hydrazine are

studied. As shown in Fig. S6, only 2.5 equiv. gas

with 81% H2 selectivity were released over 70

minutes for NiRh NPs, and almost no reactivity for

NPC-900 toward dehydrogenation of alkaline

solution of hydrazine, indicating the synergetic

effect of NPC and NiRh NPs. Furthermore, the

NiRh NPs supported on other commercial materials

are all inferior to that of Ni3Rh7/NPC-900. Moreover,

Moreover, when NiRh NPs were supported on

other carbon source, such as EC-300J, only 0.64

equiv. gases with 11.6% hydrogen selectivity was

obtained. These results further indicate the nitrogen

doping and high surface area in NPC-900 are the

dominant factor in fostering the catalytic activity of

NiRh NPs (Table S1). The stability of

NiRh@NPC-900 were tested in the decomposition of

alkaline solution by adding an additional

equivalent of hydrous hydrazine into the previous

run at 50 °C (Fig. S7). Though there exist some loss

in catalytic activity, the hydrogen selectivity

remained unchanged, and our further work on

enhancement of the stability of the as-synthesized

catalyst is still underway.

Crystalline structures of the NiRh/NPC-900 were

analysed using PXRD (Fig. S8). The diffraction

peaks of the NiRh NPs shift to higher angle

compared to that of Rh, indicating the formation of

NiRh alloy [37]. To investigate the state of Ni and

Rh, the XPS measurements were carried out and the

characteristic signal of both metal were detected

(Fig. S10), indicating the co-existence of Ni and Rh

in the Ni3Rh7/NPC-900 catalyst. The observed Rh

3d3/2 and Rh 3d5/2 peaks at 312.0 eV and 307.2 eV

correspond to the Rh0, while the observed peaks of

Ni 2p1/2 and 2p3/2 at 875.8 eV and 857.0 eV

0 5 10 15 20

Energy (keV)

C

NCu

Ni

Cu

CuRh

Figure 4 (a) HADDF-STEM image and (b,c) TEM images of

Ni3Rh7/NPC-900 , and (d) EDX spectrum.

correspond to the oxidized Ni which may be

formed during the sample preparation for XPS

measurement [38]. The BET specific surface areas of

the NPC-900 and Ni3Rh7/NPC-900 are measured

from the nitrogen adsorption-desorption isotherms

at 77 K (Fig. S9). It is found that the specific surface

area of Ni3Rh7/NPC-900 is 478.2 m2/g, which is

significantly lower than the surface area of 1996.1

m2/g for NPC-900. The significant decrease in the

amount of N2 adsorption and the pore volume of

Ni3Rh7/NPC-900 indicates that the cavities of

NPC-900 were either occupied by the well

dispersed NiRh NPs or blocked by the NiRh NPs.

The morphology of Ni3Rh7/NPC-900 was further

characterized by transmission electron microscopic

(TEM) and energy-dispersive X-ray spectroscopy

(EDX) measurements (Fig. 4), which indicates the

well-dispersed NiRh NPs with an average diameter

of 2.5 ± 0.2 nm.

4 Conclusion

In summary, for the first time, highly dispersed

NiRh NPs have been successfully immobilized on

nitrogen doped porous carbon derived from ZIF-8,

and their highly catalytic performance toward

hydrogen generation from hydrazine in alkaline

solution have been studied. Compared with

NPC-800, NPC-1000 and other commercial

supported materials, the NPC-900 supported NiRh

catalyst exhibits the highest catalytic activity and

100% hydrogen selectivity, which may be caused by

its high surface area, high graphitization and high

content of nitrogen doping. The high activity and

selectivity as well as good durability of the

ZIF-derived nitrogen doped nanoporous carbon

supported NiRh catalysts are believed to promote

the spreading use of hydrous hydrazine as a

promising chemical hydrogen storage material. The

development of high-performance catalysts by

utilizing nitrogen-doped porous carbon derived

from MOFs as a support to anchor NPs and thus to

facilitate the catalytic activity may open up a new

avenue for preparing other NPC supported metal

NPs for more applications.

Acknowledgements

This work was financially supported by the National

Natural Science Foundation of China (21201134), the

Natural Science Foundation of Jiangsu Province

(BK20130370), the Natural Science Foundation of

Hubei Province (2013CFB288), the Creative Research

Groups of Hubei Province (2014CFA007) and

Large-scale Instrument and Equipment Sharing

Foundation of Wuhan University.

Electronic Supplementary Material: Supplementary

material (further details of materials and

characterization, synthesis of ZIF-8, comparison of

different supports and durability tests ,

supplementary Tables and Figures) is available in the

online version of this article at

http://dx.doi.org/10.1007/s12274-***-****-*

(automatically inserted by the publisher).

References [1] Hamilton, C. W.; Baker, R. T.; Staubitz, A.; Manners,

http://dx.doi.org/10.1007/s12274-***-****-*


8 Nano Res.

I. B-N compounds for chemical hydrogen storage.

Chem. Soc. Rev. 2009, 38, 279-293.

[2] Yang, J.; Sudik, A.; Wolverton, C.; Siegel, D. J. High

capacity hydrogen storage materials: attributes for

automotive applications and techniques for materials

discovery. Chem. Soc. Rev. 2010, 39, 656-675.

[3] Wang, C.; Liu, D.; Lin, W. Metal-Organic

Frameworks as A Tunable Platform for Designing

Functional Molecular Materials. J. Am. Chem. Soc.

2013, 135, 13222-13234.

[4] Suh, M. P.; Park, H. J.; Prasad, T. K.; Lim, D.-W.

Hydrogen Storage in Metal-Organic Frameworks.

Chem. Rev. 2012, 112, 782-835.

[5] Luo, W.; Campbell, P. G.; Zakharov, L. N.; Liu, S.-Y.

A Single-Component Liquid-Phase Hydrogen Storage

Material. J. Am. Chem. Soc. 2011, 133, 19326-19329.

[6] Graetz, J. New approaches to hydrogen storage.

Chem. Soc. Rev. 2009, 38, 73-82.

[7] Metin, Ö.;Özkar, S.; Sun, S. Monodisperse nickel

nanoparticles supported on SiO2 as an effective

catalyst for the hydrolysis of ammonia-borane. Nano

Res. 2010, 3, 676-684.

[8] Aranishi, K.; Jiang, H.-L.; Akita, T.; Haruta, M.; Xu,

Q. One-step synthesis of magnetically recyclable

Au/Co/Fe triple-layered core-shell nanoparticles as

highly efficient catalysts for the hydrolytic dehydro-

genation of ammonia borane. Nano Res. 2011, 4,

1233-1241.

[9] Yadav, M.; Xu, Q. Liquid-phase chemical hydrogen

storage materials. Energy Environ. Sci. 2012, 5,

9698-9725.

[10] Singh, S. K.; Xu, Q. Nanocatalysts for hydrogen

generation from hydrazine. Catal. Sci. Technol. 2013,

3, 1889-1900.

[11] Song-Il, O.; Yan, J.-M.; Wang, H.-L.; Wang, Z.-L.;

Jiang, Q. High catalytic kinetic performance of

amorphous CoPt NPs induced on CeOx for H2 gener-

ation from hydrous hydrazine. Int. J. Hydrogen

Energy 2014, 39, 3755-3761.

[12] O, S.-I.; Yan, J.-M.; Wang, H.-L.; Wang, Z.-L.; Jiang,

Q. Ni/La2O3 catalyst containing low content platinum

rhodium for the dehydrogenation of N2H4·H2O at

room temperature. J. Power Sources 2014, 262,

386-390.

[13] Wang, H.-L.; Yan, J.-M.; Li, S.-J.; Zhang, X.-W.;

Jiang, Q. Noble-metal-free NiFeMo nanocatalyst for

hydrogen generation from the decomposition of

hydrous hydrazine. J. Mater. Chem. A 2015, 3,

121-124.

[14] He, L.; Liang, B.; Li, L.; Yang, X.; Huang, Y.; Wang,

A.; Wang, X.; Zhang, T. Cerium-Oxide-Modified

Nickel as a Non-Noble Metal Catalyst for Selective

Decomposition of Hydrous Hydrazine to Hydrogen.

ACS Catal. 2015, 5, 1623-1628.

[15] Li, Z.; Liu, J.; Huang, Z.; Yang, Y.; Xia, C.; Li, F.

One-Pot Synthesis of Pd Nanoparticle Catalysts

Supported on N-Doped Carbon and Application in the

Domino Carbonylation. ACS Catal. 2013, 3, 839-845.

[16] Li, Z.; Liu, J.; Xia, C.; Li, F. Nitrogen-Functionalized

Ordered Mesoporous Carbons as Multifunctional

Supports of Ultrasmall Pd Nanoparticles for Hydro-

genation of Phenol. ACS Catal. 2013, 3, 2440-2448.

[17] Qu, L.; Liu, Y.; Baek, J.-B.; Dai, L. Nitrogen-Doped

Graphene as Efficient Metal-Free Electrocatalyst for

Oxygen Reduction in Fuel Cells. ACS Nano 2010, 4,

1321-1326.

[18] Sun, J.-K.; Xu, Q. Functional materials derived from

open framework templates/precursors: synthesis and

applications. Energy Environ. Sci. 2014, 7,

2071-2100.

[19] Zhou, L.; Zhang, T.; Tao, Z.; Chen, J. Ni

nanoparticles supported on carbon as efficient

catalysts for the hydrolysis of ammonia borane. Nano

Res. 2014, 7, 774-781.

[20] Torad, N. L.; Hu, M.; Kamachi, Y.; Takai, K.; Imura,

M.; Naito, M.; Yamauchi, Y. Facile synthesis of

nanoporous carbons with controlled particle sizes by

direct carbonization of monodispersed ZIF-8 crystals.

Chem. Commun. 2013, 49, 2521-2523.

[21] Jiang, H.-L.; Liu, B.; Lan, Y.-Q.; Kuratani, K.; Akita,

T.; Shioyama, H.; Zong, F.; Xu, Q. From

Metal–Organic Framework to Nanoporous Carbon:

Toward a Very High Surface Area and Hydrogen

Uptake. J. Am. Chem. Soc. 2011, 133, 11854-11857.


9 Nano Res.

[22] Wu, R.; Qian, X.; Rui, X.; Liu, H.; Yadian, B.; Zhou,

K.; Wei, J.; Yan, Q.; Feng, X.-Q.; Long, Y.; Wang, L.;

Huang, Y. Zeolitic Imidazolate Framework

67-Derived High Symmetric Porous Co3O4 Hollow

Dodecahedra with Highly Enhanced Lithium Storage

Capability. Small 2014, 10, 1932-1938.

[23] Hu, L.;Huang, Y.;Zhang, F.; Chen, Q. CuO/Cu2O

composite hollow polyhedrons fabricated from

metal-organic framework templates for lithium-ion

battery anodes with a long cycling life. Nanoscale

2013, 5, 4186-4190.

[24] Salunkhe, R. R.; Kamachi, Y.; Torad, N. L.; Hwang, S.

M.; Sun, Z.; Dou, S. X.; Kim, J. H.; Yamauchi, Y.

Fabrication of symmetric supercapacitors based on

MOF-derived nanoporous carbons. J. Mater. Chem. A

2014, 2, 19848-19854.

[25] Meng, F.; Fang, Z.; Li, Z.; Xu, W.; Wang, M.; Liu, Y.;

Zhang, J.;Wang, W.;Zhao, D.; Guo, X. Porous Co3O4

materials prepared by solid-state thermolysis of a

novel Co-MOF crystal and their superior energy

storage performances for supercapacitors. J. Mater.

Chem. A 2013, 1, 7235-7241.

[26] Wang, J.-L.; Wang, C.; Lin, W. Metal–Organic

Frameworks for Light Harvesting and Photocatalysis.

ACS Catal.2012, 2, 2630-2640.

[27] Zhang, P.; Sun, F.; Xiang, Z.; Shen, Z.; Yun, J.; Cao,

D. ZIF-derived in situ nitrogen-doped porous carbons

as efficient metal-free electrocatalysts for oxygen

reduction reaction. Energy Environ. Sci. 2014, 7,

442-450.

[28] Zhao, S.; Yin, H.; Du, L.; He, L.; Zhao, K.; Chang, L.;

Yin, G.; Zhao, H.; Liu, S.; Tang, Z. Carbonized

Nanoscale Metal–Organic Frameworks as High

Performance Electrocatalyst for Oxygen Reduction

Reaction. ACS Nano 2014, 8, 12660-12668.

[29] Karagiaridi, O.; Lalonde, M. B.; Bury, W.; Sarjeant, A.

A.; Farha, O. K.; Hupp, J. T. Opening ZIF-8: A

Catalytically Active Zeolitic Imidazolate Framework

of Sodalite Topology with Unsubstituted Linkers. J.

Am. Chem. Soc. 2012, 134, 18790-18796.

[30] Liu, B.;Shioyama, H.;Akita, T.; Xu, Q. Metal-Organic

Framework as a Template for Porous Carbon

Synthesis. J. Am. Chem. Soc. 2008, 130, 5390-5391.

[31] Das, A.; Pisana, S.; Chakraborty, B.; Piscanec, S.;

Saha, S. K.; Waghmare, U. V.; Novoselov, K. S.;

Krishnamurthy, H. R.; Geim, A. K.; Ferrari, A. C.;

Sood, A. K. Monitoring dopants by Raman scattering

in an electrochemically top-gated graphene transistor.

Nat. Nanotechnol. 2008, 3, 210-215.

[32] Sheng, Z.-H.; Shao, L.; Chen, J.-J.; Bao, W.-J.; Wang,

F.-B.; Xia, X.-H. Catalyst-Free Synthesis of Nitrogen-

Doped Graphene via Thermal Annealing Graphite

Oxide with Melamine and Its Excellent Electro-

catalysis. ACS Nano 2011, 5, 4350-4358.

[33] Kudin, K. N.; Ozbas, B.; Schniepp, H. C.;

Prud'homme, R. K.; Aksay, I. A.; Car, R. Raman

Spectra of Graphite Oxide and Functionalized

Graphene Sheets. Nano Lett. 2008, 8, 36-41.

[34] Zhong, H.-x.; Wang, J.; Zhang, Y.-w.; Xu, W.-l.; Xing,

W.; Xu, D.; Zhang, Y.-f.; Zhang, X.-b. ZIF-8 Derived

Graphene-Based Nitrogen-Doped Porous Carbon

Sheets as Highly Efficient and Durable Oxygen

Reduction Electrocatalysts. Angew. Chem. Int. Ed.

2014, 53, 14235-14239.

[35] Wang, X.; Li, X.; Zhang, L.; Yoon, Y.; Weber, P. K.;

Wang, H.; Guo, J.; Dai, H. N-Doping of Graphene

Through Electrothermal Reactions with Ammonia.

Science 2009, 324, 768-771.

[36] Singh, S. K.; Xu, Q. Complete Conversion of

Hydrous Hydrazine to Hydrogen at Room

Temperature for Chemical Hydrogen Storage. J. Am.

Chem. Soc. 2009, 131, 18032-18033.

[37] Wang, J.; Zhang, X.-B.; Wang, Z.-L.; Wang, L.-M.;

Zhang, Y. Rhodium-nickel nanoparticles grown on

graphene as highly efficient catalyst for complete

decomposition of hydrous hydrazine at room

temperature for chemical hydrogen storage. Energy

Environ. Sci. 2012, 5, 6885-6888.

[38] Singh, A. K.;Yadav, M.;Aranishi, K.; Xu, Q.

Temperature-induced selectivity enhancement in

hydrogen generation from Rh–Ni

nanoparticle-catalyzed decomposition of hydrous

hydrazine. Int. J. Hydrogen Energy 2012, 37,

18915-18919.


10 Nano Res.

[39] Xia, B.; Cao, N.; Dai, H.; Su, J.; Wu, X.; Luo, W.;

Cheng, G. Bimetallic Nickel–Rhodium Nanoparticles

Supported on ZIF-8 as Highly Efficient Catalysts for

Hydrogen Generation from Hydrazine in Alkaline

Solution. ChemCatChem 2014, 6, 2549-2552.

[40] Singh, S. K.; Iizuka, Y.; Xu, Q. Nickel-palladium

nanoparticle catalyzed hydrogen generation from

hydrous hydrazine for chemical hydrogen storage. Int.

J. Hydrogen Energy 2011, 36, 11794-11801.

[41] Singh, S. K.; Lu, Z. H.; Xu, Q. Temperatur-Induced

Enhancement of Catalytic Performance in Selective

Hydrogen Generation from Hydrous Hydrazine with

Ni‐Based Nanocatalysts for Chemical Hydrogen

Storage. Eur. J. Inorg. Chem. 2011, 2011, 2232-2237.

[42] He, L.; Huang, Y.; Wang, A.; Liu, Y.; Liu, X.; Chen,

X.; Delgado, J. J.; Wang, X.; Zhang, T. Surface

modification of Ni/Al2O3 with Pt: Highly efficient

catalysts for H2 generation via selective

decomposition of hydrous hydrazine. J. Catal. 2013,

298, 1-9.

[43] Singh, A. K.; Xu, Q. Metal-Organic Framework

Supported Bimetallic NiPt Nanoparticles as High

performance Catalysts for Hydrogen Generation from

Hydrazine in Aqueous Solution. ChemCatChem 2013,

5, 3000-3004.

[44] Wang, H.-L.; Yan, J.-M.; Wang, Z.-L.; O, S.-I.; Jiang,

Q. Highly efficient hydrogen generation from

hydrous hydrazine over amorphous Ni0.9Pt0.1/Ce2O3

nanocatalyst at room temperature. J. Mater. Chem. A

2013, 1, 14957-14962.

[45] Singh, S. K.; Xu, Q. Bimetallic nickel-iridium

nanocatalysts for hydrogen generation by

decomposition of hydrous hydrazine. Chem. Commun.

2010, 46, 6545-6547.

[46] Aijaz, A.; Fujiwara, N.; Xu, Q. From Metal–Organic

Framework to Nitrogen-Decorated Nanoporous Carb-

ons: High CO2 Uptake and Efficient Catalytic

Oxygen Reduction. J. Am. Chem. Soc. 2014, 136,

6790-6793.

nirh nanoparticles supported on nitrogen-doped porous

Documents