layered 2d advanced materials - download.e-bookshelf.de · this edition first published 2020 by...

Layered 2D Advanced Materials and Their Allied Applications

Scrivener Publishing100 Cummings Center, Suite 541J

Beverly, MA 01915-6106

Publishers at ScrivenerMartin Scrivener ([email protected])

Phillip Carmical ([email protected])

Scrivener Publishing100 Cummings Center, Suite 541J

Beverly, MA 01915-6106

Publishers at ScrivenerMartin Scrivener ([email protected])

Phillip Carmical ([email protected]) Layered 2D Advanced Materials and Their Allied Applications

Edited by Inamuddin, Rajender Boddula,

Mohd Imran Ahamed and Abdullah M. Asiri

This edition first published 2020 by John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, USA and Scrivener Publishing LLC, 100 Cummings Center, Suite 541J, Beverly, MA 01915, USA© 2020 Scrivener Publishing LLCFor more information about Scrivener publications please visit www.scrivenerpublishing.com.

All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording, or other-wise, except as permitted by law. Advice on how to obtain permission to reuse material from this title is available at http://www.wiley.com/go/permissions.

Wiley Global Headquarters111 River Street, Hoboken, NJ 07030, USA

For details of our global editorial offices, customer services, and more information about Wiley prod-ucts visit us at www.wiley.com.

Limit of Liability/Disclaimer of WarrantyWhile the publisher and authors have used their best efforts in preparing this work, they make no rep-resentations or warranties with respect to the accuracy or completeness of the contents of this work and specifically disclaim all warranties, including without limitation any implied warranties of merchant- ability or fitness for a particular purpose. No warranty may be created or extended by sales representa-tives, written sales materials, or promotional statements for this work. The fact that an organization, website, or product is referred to in this work as a citation and/or potential source of further informa-tion does not mean that the publisher and authors endorse the information or services the organiza-tion, website, or product may provide or recommendations it may make. This work is sold with the understanding that the publisher is not engaged in rendering professional services. The advice and strategies contained herein may not be suitable for your situation. You should consult with a specialist where appropriate. Neither the publisher nor authors shall be liable for any loss of profit or any other commercial damages, including but not limited to special, incidental, consequential, or other damages. Further, readers should be aware that websites listed in this work may have changed or disappeared between when this work was written and when it is read.

Library of Congress Cataloging-in-Publication Data

ISBN 978-1-119-65496-4

Cover image: Pixabay.ComCover design by Russell Richardson

Set in size of 11pt and Minion Pro by Manila Typesetting Company, Makati, Philippines

Printed in the USA

10 9 8 7 6 5 4 3 2 1

v

Contents

Preface xv1 2D Metal-Organic Frameworks 1

Fengxian Cao, Jian Chen, Qixun Xia and Xinglai Zhang1.1 Introduction 11.2 Synthesis Approaches 2

1.2.1 Selection of Synthetic Raw Materials 31.2.2 Solvent Volatility Method 41.2.3 Diffusion Method 4

1.2.3.1 Gas Phase Diffusion 41.2.3.2 Liquid Phase Diffusion 4

1.2.4 Sol-Gel Method 51.2.5 Hydrothermal/Solvothermal Synthesis Method 61.2.6 Stripping Method 61.2.7 Microwave Synthesis Method 81.2.8 Self-Assembly 91.2.9 Special Interface Synthesis Method 91.2.10 Surfactant-Assisted Synthesis Method 101.2.11 Ultrasonic Synthesis 10

1.3 Structures, Properties, and Applications 111.3.1 Structure and Properties of MOFs 111.3.2 Application in Biomedicine 121.3.3 Application in Gas Storage 121.3.4 Application in Sensors 131.3.5 Application in Chemical Separation 131.3.6 Application in Catalysis 141.3.7 Application in Gas Adsorption 14

1.4 Summary and Outlook 15 Acknowledgements 16 References 16

vi Contents

2 2D Black Phosphorus 21Chenguang Duan, Hui Qiao, Zongyut Huang and Xiang Qi2.1 Introduction 222.2 The Research on Black Phosphorus 23

2.2.1 The Structure and Properties 232.2.1.1 The Structure of Black Phosphorus 252.2.1.2 The Properties of Black Phosphorus 25

2.2.2 Preparation Methods 262.2.2.1 Mechanical Exfoliation 282.2.2.2 Liquid-Phase Exfoliation 28

2.2.3 Antioxidant 302.2.3.1 Degradation Mechanism 302.2.3.2 Adding Protective Layer 312.2.3.3 Chemical Modification 312.2.3.4 Doping 33

2.3 Applications of Black Phosphorus 332.3.1 Electronic and Optoelectronic 34

2.3.1.1 Field-Effect Transistors 342.3.1.2 Photodetector 35

2.3.2 Energy Storage and Conversion 362.3.2.1 Catalysis 362.3.2.2 Batteries 372.3.2.3 Supercapacitor 38

2.3.3 Biomedical 392.4 Conclusion and Outlook 40 Acknowledgements 41 References 41

3 2D Metal Carbides 47Peiran Hou, Xinxin Fu, Qixun Xia and Zhengpeng Yang3.1 Introduction 473.2 Synthesis Approaches 48

3.2.1 Ti3C2 Synthesis 483.2.2 V2C Synthesis 503.2.3 Ti2C Synthesis 503.2.4 Mo2C Synthesis 51

3.3 Structures, Properties, and Applications 523.3.1 Structures and Properties of 2D Metal Carbides 52

3.3.1.1 Structures and Properties of Ti3C2 523.3.1.2 Structural Properties of Ti2C 533.3.1.3 Structural Properties of Mo2C 53

Contents vii

3.3.1.4 Structural Properties of V2C 543.3.2 Carbide Materials in Energy Storage Applications 55

3.3.2.1 Ti3C2 563.3.2.2 Ti2C 573.3.2.3 V2C 583.3.2.4 Mo2C 58

3.3.3 Metal Carbide Materials in Catalysis Applications 603.3.3.1 Ti3C2 603.3.3.2 V2C 613.3.3.3 Mo2C 62

3.3.4 Metal Carbide Materials in Environmental Management Applications 633.3.4.1 Ti3C2 in Environmental Management

Applications 633.3.4.2 Ti2C in Environmental Management

Applications 643.3.4.3 V2C in Environmental Management

Applications 643.3.4.4 Mo2C in Environmental Management

Applications 653.3.5 Carbide Materials in Biomedicine Applications 66

3.3.5.1 Ti3C2 in Biomedicine Applications 663.3.5.2 Ti2C in Biomedicine Applications 663.3.5.3 V2C in Biomedicine Applications 683.3.5.4 Mo2C in Biomedicine Applications 68

3.3.6 Carbide Materials in Gas Sensing Applications 693.3.6.1 Ti3C2 in Gas Sensing Applications 693.3.6.2 Ti2C in Gas Sensing Applications 693.3.6.3 V2C in Gas Sensing Applications 703.3.6.4 Mo2C in Gas Sensing Applications 71

3.4 Summary and Outlook 72 Acknowledgements 72 References 73

4 2D Carbon Materials as Photocatalysts 79Amel Boudjemaa4.1 Introduction 794.2 Carbon Nanostructured-Based Materials 80

4.2.1 Forms of Carbon 804.2.2 Synthesis of Carbon Nanostructured-Based Materials 80

4.3 Photo-Degradation of Organic Pollutants 81

viii Contents

4.3.1 Graphene, Graphene Oxide, Graphene Nitride (g-C3N4) 814.3.1.1 Graphene-Based Materials 824.3.1.2 Graphene Nitride (g-C3N4) 84

4.3.2 Carbon Dots (CDs) 874.3.3 Carbon Spheres (CSs) 87

4.4 Carbon-Based Materials for Hydrogen Production 884.5 Carbon-Based Materials for CO2 Reduction 90 References 90

5 Sensitivity Analysis of Surface Plasmon Resonance Biosensor Based on Heterostructure of 2D BlueP/MoS2 and MXene 103Sarika Pal, Narendra Pal, Y.K. Prajapati and J.P. Saini5.1 Introduction 1045.2 Proposed SPR Sensor, Design Considerations, and Modeling 107

5.2.1 SPR Sensor and Its Sensing Principle 1075.2.2 Design Consideration 108

5.2.2.1 Layer 1: Prism for Light Coupling 1085.2.2.2 Layer 2: Metal Layer 1095.2.2.3 Layer 3: BlueP/MoS2 Layer 1105.2.2.4 Layer 4: MXene (Ti3C2Tx) Layer as BRE

for Biosensing 1105.2.2.5 Layer 5: Sensing Medium (RI-1.33-1.335) 110

5.2.3 Proposed Sensor Modeling 1105.3 Results Discussion 112

5.3.1 Role of Monolayer BlueP/MoS2 and MXene (Ti3C2Tx) and Its Comparison With Conventional SPR 112

5.3.2 Influence of Varying Heterostructure Layers for Proposed Design 114

5.3.3 Effect of Changing Prism Material and Metal on Performance of Proposed Design 115

5.4 Conclusion 125 References 125

6 2D Perovskite Materials and Their Device Applications 131B. Venkata Shiva Reddy, K. Srinivas, N. Suresh Kumar, S. Ramesh, K. Chandra Babu Naidu, Prasun Banerjee, Ramyakrishna Pothu and Rajender Boddula6.1 Introduction 1316.2 Structure 134

6.2.1 Crystal Structure 1346.2.2 Electronic Structure of 2D Perovskites 134

Contents ix

6.2.3 Structure of Photovoltaic Cell 1356.3 Discussion and Applications 1366.4 Conclusion 139 References 139

7 Introduction and Significant Parameters for Layered Materials 141Umbreen Rasheed, Fayyaz Hussain, Muhammad Imran, R.M. Arif Khalil and Sungjun Kim7.1 Graphene 1437.2 Phosphorene 1477.3 Silicene 1487.4 ZnO 1507.5 Transition Metal Dichalcogenides (TMDCs) 1517.6 Germanene and Stanene 1527.7 Heterostructures 153 References 156

8 Increment in Photocatalytic Activity of g-C3N4 Coupled Sulphides and Oxides for Environmental Remediation 159Pankaj Raizada, Abhinadan Kumar and Pardeep Singh 8.1 Introduction 1608.2 GCN Coupled Metal Sulphide Heterojunctions

for Environment Remediation 1638.2.1 GCN and MoS2-Based Photocatalysts 1638.2.2 GCN and CdS-Based Heterojunctions 1688.2.3 Some Other GCN Coupled Metal Sulphide

Photocatalysts 1718.3 GCN Coupled Metal Oxide Heterojunctions

for Environment Remediation 1738.3.1 GCN and MoO3-Based Heterojunctions 1778.3.2 GCN and Fe2O3-Based Heterojunctions 1798.3.3 Some Other GCN Coupled Metal Oxide

Photocatalysts 1808.4 Conclusions and Outlook 181 References 181

9 2D Zeolites 193Moumita Sardar, Manisha Maharana, Madhumita Manna and Sujit Sen9.1 Introduction 193

9.1.1 What is 2D Zeolite? 1959.1.2 Advancement in Zeolites to 2D Zeolite 196

x Contents

9.2 Synthetic Method 1979.2.1 Bottom-Up Method 1979.2.2 Top-Down Method 1989.2.3 Support-Assisted Method 1999.2.4 Post-Synthesis Modification of 2D Zeolites 200

9.3 Properties 2009.4 Applications 203

9.4.1 Petro-Chemistry 2039.4.2 Biomass Conversion 203

9.4.2.1 Pyrolysis of Solid Biomass 2039.4.2.2 Condensation Reactions 2049.4.2.3 Isomerization 2049.4.2.4 Dehydration Reactions 204

9.4.3 Oxidation Reactions 2059.4.4 Fine Chemical Synthesis 2069.4.5 Organometallics 206


10 2D Hollow Nanomaterials 211 S.S. Athira, V. Akhil, X. Joseph , J. Ashtami and P.V. Mohanan10.1 Introduction 21210.2 Structural Aspects of HNMs 21310.3 Synthetic Approaches 214

10.3.1 Template-Based Strategies 21510.3.1.1 Hard Templating 21510.3.1.2 Soft Templating 217

10.3.2 Self-Templating Strategies 21810.3.2.1 Surface Protected Etching 21910.3.2.2 Ostwald Ripening 21910.3.2.3 Kirkendall Effect 21910.3.2.4 Galvanic Replacement 220

10.4 Medical Applications of HNMs 22010.4.1 Imaging and Diagnosis Applications 22110.4.2 Applications of Nanotube Arrays 222

10.4.2.1 Pharmacy and Medicine 22410.4.2.2 Cancer Therapy 22410.4.2.3 Immuno and Hyperthermia Therapy 22610.4.2.4 Infection Therapy and Gene Therapy 226

10.4.3 Hollow Nanomaterials in Diagnostics and Therapeutics 227

Contents xi

10.4.4 Applications in Regenerative Medicine 22710.4.5 Anti-Neurodegenerative Applications 22810.4.6 Photothermal Therapy 22910.4.7 Biosensors 230

10.5 Non-Medical Applications of HNMs 23110.5.1 Catalytic Micro or Nanoreactors 23110.5.2 Energy Storage 232

10.5.2.1 Lithium Ion Battery 23210.5.2.2 Supercapacitor 232

10.5.3 Nanosensors 23310.5.4 Wastewater Treatment 234

10.6 Toxicity of 2D HNMs 23410.7 Future Challenges 23710.8 Conclusion 239 Acknowledgement 240 References 240

11 2D Layered Double Hydroxides 249J. Ashtami, X. Joseph, V. Akhil , S.S. Athira and P.V. Mohanan11.1 Introduction 25011.2 Structural Aspects 25111.3 Synthesis of LDHs 252

11.3.1 Co-Precipitation Method 25311.3.2 Urea Hydrolysis 25411.3.3 Ion-Exchange Method 25411.3.4 Reconstruction Method 25411.3.5 Hydrothermal Method 25511.3.6 Sol-Gel Method 255

11.4 Nonmedical Applications of LDH 25511.4.1 Adsorbent 25511.4.2 Catalyst 25711.4.3 Sensors 26011.4.4 Electrode 26111.4.5 Polymer Additive 26111.4.6 Anion Scavenger 26211.4.7 Flame Retardant 263

11.5 Biomedical Applications 26311.5.1 Biosensors 26311.5.2 Scaffolds 26511.5.3 Anti-Microbial Agents 26611.5.4 Drug Delivery 267

xii Contents

11.5.5 Imaging 26911.5.6 Protein Purification 26911.5.7 Gene Delivery 270

11.6 Toxicity 27211.7 Conclusion 273 Acknowledgement 274 References 274

12 Experimental Techniques for Layered Materials 283Tariq Munir, Arslan Mahmood, Muhammad Imran, Muhammad Kashif, Amjad Sohail, Zeeshan Yaqoob, Aleena Manzoor and Fahad Shafiq 12.1 Introduction 28412.2 Methods for Synthesis of Graphene Layered Materials 28512.3 Selection of a Suitable Metallic Substrate 28712.4 Graphene Synthesis by HFTCVD 28712.5 Graphene Transfer 28912.6 Characterization Techniques 291

12.6.1 X-Ray Diffraction Technique 29112.6.2 Field Emission Scanning Electron Microscopy

(FESEM) 29212.6.3 Transmission Electron Microscopy (TEM) 29312.6.4 Fourier Transform Infrared Radiation (FTIR) 29412.6.5 UV-Visible Spectroscopy 29512.6.6 Raman Spectroscopy 29512.6.7 Low Energy Electron Microscopy (LEEM) 296

12.7 Potential Applications of Graphene and Derived Materials 29712.8 Conclusion 298 Acknowledgement 298 References 299

13 Two-Dimensional Hexagonal Boron Nitride and Borophenes 303Atif Suhail and Indranil Lahiri13.1 Two-Dimensional Hexagonal Boron Nitride (2D h-BN):

An Introduction 30413.2 Properties of 2D h-BN 305

13.2.1 Structural Properties 30513.2.2 Electronic and Dielectric Properties 30613.2.3 Optical Properties 307

13.3 Synthesis Methods of 2D h-BN 30813.3.1 Mechanical Exfoliation 309

Contents xiii

13.3.2 Liquid Exfoliation 31013.3.3 Chemical Vapor Deposition (CVD) 310

13.3.3.1 Synthesis Parameters 31213.3.3.2 Growth Mechanism 31313.3.3.3 Transfer of 2D h-BN Onto

Other Substrates 31413.3.4 Physical Vapor Deposition Method (PVD) 31513.3.5 Surface Segregation Method 316

13.4 Application of 2D h-BN 31713.4.1 2D h-BN in Electronic Manufacturing 31813.4.2 2D h-BN as a Filler in Polymer Composites 31913.4.3 2D h-BN as a Protective Barrier 32013.4.4 2D h-BN in Optoelectronics 321

13.5 Borophene 32313.5.1 Theoretical Investigation and Experimental

Synthesis 32413.5.2 Properties and Application of Borophene 326

13.5.2.1 Electronic Properties of Borophene 32613.5.2.2 Chemical Properties 326

13.5.3 Potential Applications of Borophene 328 References 328

14 Transition-Metal Dichalcogenides for Photoelectrochemical Hydrogen Evolution Reaction 337Rozan Mohamad Yunus, Mohd Nur Ikhmal Salehmin and Nurul Nabila Rosman14.1 Introduction 33714.2 TMDC-Based Photoactive Materials for HER 339

14.2.1 MoS2 33914.2.2 MoSe2 34114.2.3 WS2 34114.2.4 CoSe2 34214.2.5 FeS2 34314.2.6 NiSe2 344

14.3 TMDCs Fabrication Methods 34514.3.1 Hydrothermal 34514.3.2 Chemical Vapor Deposition/Vapor Phase

Growth Process 34614.3.3 Metal-Organic Chemical Vapor Deposition

(MOCVD) 34714.3.4 Atomic Layer Deposition (ALD) 348

xiv Contents

14.4 Current Photocatalytic Activity Performance 35014.5 Summary and Perspective 351 References 352

15 State-of-the-Art and Perspective of Layered Materials 363Tariq Munir, Muhammad Kashif, Aamir Shahzad, Nadeem Nasir, Muhammad Imran, Nabeel Anjum and Arslan Mahmood

15.1 Introduction 36315.2 State-of-the-Art and Future Perspective 364

15.2.1 Electronic Devices 36515.2.2 Optoelectronic Devices 36915.2.3 Energy Storage Devices 372


Index 379

xv

Preface

Ever since the discovery of graphene, two-dimensional layered materials (2DLMs) have been the central tool of the materials research community. The reason behind their importance is their superlative and unique elec-tronic, optical, physical, chemical, and mechanical properties in layered form rather than in bulk form. The 2DLMs have been applied to electron-ics, catalysis, energy, environment, and biomedical applications.

Layered Advanced Materials and Their Allied Applications is an in-depth exploration of 2DLMs and their applications, including fabrication and characterization methods. It also provides the fundamentals, challenges, as well as perspectives on their practical applications. The comprehensive chapters herein are written by various materials science experts from all over the world. Therefore, this book is an essential reference guide for junior research scholars, faculty members, engineers, and professionals interested in materials science applications. The following topics are dis-cussed in the book’s 15 chapters:

Chapter 1 discusses the research status and development prospects for 2D metal-organic frameworks and the different techniques used to synthe-size them. The advantages and limitations of these methods are summa-rized. Also, the structure, characteristics, and various applications of 2D metal-organic frameworks are mentioned.

Chapter 2 mainly discusses the research on 2D black phosphorus (BP) and its application in various fields. Several studies on 2D BP are introduced, including its properties and structures, preparation methods, and antioxi-dants. The major focus is given to communicating the advantages of 2D BP in practical applications.

xvi Preface

Chapter 3 reviews the synthesis methods of MXenes and provides a detailed discussion of their structural characterization and physical, electrochem-ical, and optical properties. The major focus is given to introducing the applications of MXenes in catalysis, energy storage, environmental man-agement, biomedicine, and gas sensing.

Chapter 4 describes the carbon-based materials and their potential appli-cations via the photocatalytic process using visible light irradiation. Furthermore, 2D carbon-based materials are described for most large-scale photocatalytic applications mentioned in the literature for addressing environmental issues such as pollutant degradation, heavy metal elimina-tion, hydrogen (H2) generation, and CO2 reduction.

Chapter 5 discusses the importance of 2D materials like graphene, TMDCs, few-layer phosphorene, MXene in layered form, and their heterostruc-tures. It analyzes the sensitivity of surface plasmon resonance (SPR) bio-sensor based on heterostructure of 2D blueP/MoS2 and MXene (Ti3C2Tx). Their performance is analyzed for the different number of heterostructure layers and different prisms in the visible region.

Chapter 6 summarizes the structure and applications of 2D perovskites.

Chapter 7 details the exotic properties of layered materials. Physical parameters of pristine layered materials, ZnO, transition metal dichal-cogenides, and heterostructures of layered materials are discussed. All parameters are calculated using density functional theory employing Vienna ab initio simulation package. The major focus of this chapter is on the significant parameters and intriguing applications of layered materials.

Chapter 8 describes the coupling of graphitic carbon nitride with various metal sulfides and oxides to form efficient heterojunction for water puri-fication. The optical band edge alignments and mechanistic viewpoint of charge migration and space separation are also explored. Finally, chal-lenges in the proposed field are also discussed.

Chapter 9 details the structural features, synthetic methods, proper-ties, and different applications of 2D zeolites. It gives a brief account of advancements in 2D zeolites. Different synthetic methods of 2D zeolites,

Preface xvii

their properties, and various applications especially as a catalyst in differ-ent types of reactions are also elaborated in the chapter.

Chapter 10 discusses the importance and scope of 2D hollow nanomateri-als. The methods for synthesizing hollow nanostructures are featured and their structural aspects and potential in medical and nonmedical applica-tions are highlighted. Furthermore, the challenges and futuristic perspec-tive of these nanomaterials are mentioned.

Chapter 11 features the characteristics and structural aspects of 2D lay-ered double hydroxides (LDHs). The various synthesis methods and role of LDH in nonmedical applications as adsorbent, sensor, catalyst, etc., are discussed. Besides which, the application scope and biocom-patibility of LDH in various biomedical applications are focused on in detail.

Chapter 12 primarily focuses on the synthesis of graphene-based 2D lay-ered materials. Such materials can be synthesized using top-down and bottom-up approaches where the main emphasis is on the hot-filament thermal chemical vapor deposition (HFTCVD) method. Moreover, the characterization techniques, including X-ray powder diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission elec-tron microscopy (TEM), Fourier-transform infrared spectroscopy (FTIR), UV-Vis spectroscopy, Raman spectroscopy, and low-energy electron microscopy (LEEM), are discussed.

Chapter 13 discusses the different properties of 2D h-BN and borophene in detail. The chapter also includes various methods being used for the synthesis of 2D h-BN, along with their growth mechanism and transfer techniques. Applications like electronics, fillers in polymer composite, and protective barrier are also discussed in detail.

Chapter 14 discusses the physical properties and current progress of vari-ous transition metal dichalcogenides (TMDC) based on photoactive mate-rials for photoelectrochemical (PEC) hydrogen evolution reaction. Besides which, an overview of TMDC fabrication methods is presented and mit-igation of an issue related to TMDC as a photocatalyst for PEC hydrogen evolution reaction is addressed.

xviii Preface

Chapter 15 focuses on the state of the art and perspective of 2D layered materials and associated devices, such as electronic, biosensing, optoelec-tronic, and energy storage applications, due to their excellent properties. Moreover, recent developments in this area are discussed and perspectives on future developments are offered.

EditorsInamuddin

Rajender BoddulaMohd Imran Ahamed

Abdullah M. AsiriFebruary 2020

1

Inamuddin, Rajender Boddula, Mohd Imran Ahamed and Abdullah M. Asiri (eds.) Layered 2D Advanced Materials and Their Allied Applications, (1–20) © 2020 Scrivener Publishing LLC

1

2D Metal-Organic FrameworksFengxian Cao1‡, Jian Chen1‡, Qixun Xia1* and Xinglai Zhang2†

1Henan Key Laboratory of Materials on Deep-Earth Engineering, School of Materials Science and Engineering, Henan Polytechnic University,

Jiaozuo, China2Shenyang National Laboratory for Materials Science (SYNL), Institute of Metal

Research (IMR), Chinese Academy of Sciences (CAS), Shenyang, China

AbstractThe metal organic framework (MOF) is a crystalline porous material formed of an inorganic metal ion or cluster and an organic ligand. The invention has the char-acteristics of large pore volume, high specific surface area, variable structures, and multiple functions. It was widely applied in the fields of gas storage, separation, catalysis, sensing, and biomedicine. The emergence of this kind of material, to a large extent, has provided opportunities for the common development of other disciplines. In this chapter, the recent research and development of MOFs materi-als, including the synthesis methods (sol-gel method, hydrothermal solvothermal method, and microwave synthesis, etc.), the development status, the applications, i.e., hydrogen storage, energy storage, gas adsorption, catalytic reaction, sensors, biomedical applications, and so on, and the research hotspots of MOFs will be addressed.

Keywords: MOF, biomedicine, gas storage, sensors, catalysis

1.1 Introduction

Amidst the highly porous materials, metal organic frameworks (MOFs) exhibited incomparable tunable and structural diversity. Furthermore, MOFs

*Corresponding author: [email protected]†Corresponding author: [email protected]‡The authors contributed equally

2 Layered 2D Advanced Materials and Their Allied Applications

synchronously demonstrate porosity and excellent electrical conductivity, which are a burgeoning group of materials and provide a wide range of applications, for instance, energy storages, electrocatalytic oxidation, gas adsorption, biomedical [1–6]. The atomic-level control over molecular and supramolecular structure provided by MOFs gives the chance for exploit-ing some new materials for a variety of applications [7].

As a new type of porous inorganic-organic hybrid crystal material, MOFs materials have attracted extensive attention in chemistry, material, physics, and other fields. It combines the characteristics of inorganic and organic materials. It has a wide range of potential values in gas storage and separation, luminous, sensing, catalysis, magnetism, and other fields. When MOFS was made into membrane, the application of MOFs mate-rial in gas phase field was expanded. The gas separation application of MOFs extends from adsorption separation to membrane separation. By using the adjustable or modified characteristics of pore size, shape, and surface chemical properties of MOFs, MOFs material is endowed with better membrane separation performance for some light gas molecules. In addition, MOFs film extends the detection range of MOFs to gas, which can realize humidity detection and fluorescence detection of other gases or vapors. In these cases, the MOFs will play an important role in the genera-tion, transmission, adsorption, and storage.

The objective of this chapter is to summary recent literature describing the progress of MOFs. We first review the technology about how to grow MOFs thin films, including sol-gel method, hydrothermal solvothermal method, and microwave synthesis, etc. Whereafter, we summarized the structural feature and physicochemical properties description of MOFs. Subsequent sections discuss the MOF films in various applications, includ-ing hydrogen storage, energy storage, gas adsorption, catalytic reaction, sensors, biomedical applications, and the like. Finally, we discuss some limitations of MOFs in practical application.

1.2 Synthesis Approaches

The synthesis of two-dimensional (2D) MOFs compounds materials is gen-erally carried out by cultivating single crystals. X-ray single crystal struc-ture analysis is the most important method to determine the structure of metallic organic skeleton materials [8]. The accurate molecular structure of organometallic skeleton materials can be obtained by analysis. At present, the methods of synthesizing organometallic skeleton materials reported in the literature mainly include solution volatilization method, diffusion

2D Metal-Organic Frameworks 3

method, and hydrothermal/solvothermal synthesis route. These methods complement each other and sometimes use different synthesis methods or the same method and different conditions to obtain materials with different structures and functions [9]. With the development of collocation chemis-try and material chemistry, ultrasonic synthesis, ion-liquid method, solid phase reaction method, sublimation method, microwave synthesis, method and two-phase synthesis method have also been applied to the synthesis of MOFs materials. Various synthesis ways have their own advantages and disadvantages. Therefore, the choice of synthesis methods is very important for the synthesis of MOFs, and even affects its structure and properties.

1.2.1 Selection of Synthetic Raw Materials

When the synthesis of MOFs is started, it is important to maintain the integrity of skeleton looseness in addition to geometric factors. Therefore, it is necessary to find sufficient mild conditions to maintain the function and structure of the organic ligand, while having sufficient reactivity to establish the coordination bond between the metal and the organic [10].

First of all, the metal components are mainly transition metal ions, and most of the valence states used by Zn2+, Cu2+, Ni2+, Pd2+, Pt2+, Ru, and Co2+. Secondly, organic ligands should contain at least one multi-dentate functional group, such as CO2H, CS2H, NO2, SO3H, and PO3H. CO2H was more commonly used in multi-dentate functional groups, such as ereph-thalic acid (BDC), tribenzoic acid (BTC), oxalic acid, succinic acid, etc. The selection of suitable organic ligands can not only form MOFs with novel structure, but also produce special physical properties. In addition, solvents can dissolve and protonize ligands in the process of synthesis. Metal salt and most ligands are solid as solvent is needed to dissolve it. Before metal ions and ligands are coordinated, ligands (such as carboxylic acids) need to be deprotonized, so alkaline solvents are often used. At present, many deprotonated alkaloids are used as organic amines, such as triethylamine (TEA), N, N2 dimethyl formamide (DMF), N, N2 dieth-ylamide (DEF), N2 methyl pyrrolidone. At the same time, they are good solvents. In recent years, there are gradually examples of deprotonation with strong bases such as sodium hydroxide. Sometimes, solvents can also coordinate with metal ions as ligands or form weak interactions with other ligands, such as hydrogen bonds, which can be excluded by heat-ing and vacuum. Finally, in order to make the synthesized organometallic skeleton have ideal pores, it is necessary to select the appropriate template reagent. Template reagents are sometimes separate substances, sometimes the solvents used.


1.2.2 Solvent Volatility Method

Solvent volatility method is suitable for the metal salt and ligands with good solubility and the obtained products that have a poor solubility in the used solvent. If the solubility of the ligands is poor, the dissolution of the ligands can be promoted by proper heating, and the coordination reaction can also be accelerated. The crystallization of the obtained coordination products is precipitated in the process of cooling [10, 11].

Solvent volatilization method is the most traditional method to synthe-size MOFs materials and the principle of this method is that the crystal precipitates from saturated solution by solvent volatilization or decreasing temperature, and slowing down the volatilization rate or cooling is benefi-cial to the cultivation of perfect crystal form [12].

Specifically, by dissolving the selected organic ligands and metal salts in the appropriate solvent and placing them at rest, waiting for their slow self-assembly to form complex crystals.

1.2.3 Diffusion Method

Diffusion method means that the metal salt organic ligands and solvents are mixed into solution in a certain proportion, put into a small glass bottle that is placed in a large bottle with deproteinized solvent, seal the bottle mouth of the large bottle, and then the crystal can be formed after a period of static setting. Diffusion methods can be divided into gas phase diffusion, liquid layer diffusion, and gel diffusion.

1.2.3.1 Gas Phase Diffusion

The gas phase diffusion method is to dissolve the selected organic ligands and metal salt in the appropriate solvent, and then cause the lazy vola-tile solvent or volatile alkaline substance (for the carboxylic acid ligand containing hydrogen protons) to diffuse into the solution to reduce the solubility of the obtained complex product or speed up the coordination reaction, so that the complex precipitates in the form of crystallization. The volatilization rate of volatile solvents or alkaline substances in gas phase diffusion method will affect the nucleation speed of the complexes, and then affect the quality of precipitated crystals.

1.2.3.2 Liquid Phase Diffusion

The liquid phase diffusion method is to dissolve the selected organic ligands and metal salt in different solvents, and then put the seed solution


on top of the other solution, or add another solvent to the interface of the two layers of solution that can slow down the diffusion rate. The reactant diffuses slowly and reacts in the solvent, and the reaction product precip-itates in the form of crystal. The diffusion rate of reactants in liquid phase diffusion method will affect the morphology of the precipitated crystals.

In general, the diffusion method is mild and it is easy to obtain high-quality single crystal, but it is time-consuming and the solubility of reactants is required to be better and can be dissolved at room temperature.

1.2.4 Sol-Gel Method

The sol-gel method is to use the compounds containing high chemical active components as precursors, which are uniformly mixed in liquid phase, hydrolyzed and condensed, and form a steady transparent sol sys-tem in the solution. In this process, the sol was slowly polymerized between aging colloidal particles to form a three-dimensional (3D) network struc-ture gel before the network was filled with illiquid solvents to form a gel. After drying, sintering, and curing, the gel prepared molecular and even nano-substructure materials [13].

In 2017, Tian et al. [14] synthesized a porous monolithic metal-organic framework monoHKUST-1 (Cu3(BTC)2(H2O)3, BTC = 1,3,5-benzenetricar-boxylate) by a sol-gel process. In the reaction process, the crystal primary MOFs particles were first formed, then the mother liquor was centrifuged, and the dense solid (gel) was washed for removing the unreacted precursors.

In summary, sol-gel method demonstrated following advantages: 1) The reactants may be uniformly mixed at the molecular level when the gel was formed as the primary materials utilized in the sol-gel method were first disseminate to the solvent for forming a lower viscosity solution, the uni-formity at the molecular level can be obtained in a very short period of time. 2) In the step of solution reaction, add a small amount of elements, what is needed to achieve uniform doping of 2D metal-organic skeleton at the molecular level. 3) The reaction temperature required for sol-gel synthesis is lower, so it is easier to carry out the reaction than the solid state reac-tion [15]. What’s more, the components in the sol-gel system were diffused in the nanometer range, while the components in the solid state reaction were diffused in the micron range, so the reaction of the sol-gel system is easy and the reaction temperature is low. 4) Various new 2D metal-organic frameworks materials can be prepared by selecting suitable conditions. On the other hand, sol-gel method’s disadvantages are described as follows: 1) the used raw materials are more expensive, some organic materials are harmful to health; 2) the whole sol-gel process usually takes a long time,


often taking a few days or weeks; 3) there are a number of micropores in the gel, which will escape a lot of gases and organic matter and produce shrinkage in the drying process of 2D metal-organic frameworks [16].

1.2.5 Hydrothermal/Solvothermal Synthesis Method

Hydrothermal/solvothermal synthesis is the most effective way to syn-thesize MOFs that refers to the fact that ligands, metal salt, and reaction solvent are put into the reaction vessel together. At high temperature and high pressure (generally below 3,000 C) [12], the difference of solubility of each component is minimized and the viscosity of solvent decreases and the diffusion effect is strengthened which makes the complex tend to crys-tallization and precipitate. Large skeleton organic ligands with low solubil-ity at room temperature and pressure are very suitable for hydrothermal/solvothermal method. In general, the crystals synthesized by this method are easier to generate high-dimensional frame structures than the reac-tions at room temperature. According to the different reaction vessels used in the synthesis process of hydrothermal/solvothermal method, they can be divided into two common methods: reaction kettle and pipe sealing [17, 18]. Zheng et al. [19] synthesized a series of novel POMMOFs from {Ni6PW9} cluster with 2D structure under a hydrothermal route.

Li et al. [20] synthesized flake MOF-2, with zinc ion and terephthalic acid in different solvents. This kind of flake material with 1.5–6 nm thick-ness, and they found that, if different solvents were used, the thickness of the prepared nanoparticles was different. After comparing methanol, ethanol, acetone, and DMF as solvents, it was found that the nanoparticles were the thinnest when acetone was used as solvent, and the monodisperse nanoparticles prepared would not regroup.

This method has a short reaction time and solves the problem that the reactants cannot be dissolved at room temperature. The solvents used in the synthesis, especially the organic solvents, have different functional groups. Different polarity, different dielectric constant, different boiling point and viscosity can greatly increase the diversity of synthesis route and product structure. Solvothermal growth technology has perfect crystal growth. Equipment simply saves energy and other advantages, so it has become a hot spot in recent years.

1.2.6 Stripping Method

Peeling 3D layered organometallic skeleton (MOFs) from top to bot-tom is one of the effective ways to control the preparation of ultra-thin


organometallic nanoparticles on a large scale, because the interlaminar interaction force is weak van der Waals force or hydrogen bond, and peel-ing can be realized by simple mechanical grinding or ultrasonic method.

Junggeburth et al. [21] use CTAB as surfactants, 1-hexyl alcohol and water as mixed phase microemulsion method. ZnBIM 2D organic com-plexes with lamellar accumulation were prepared from zinc acetate and benzimidazole. The single layer of the coordination polymer is only 2.6 nm, and the monolayer polymer plus surfactants layer is only 5.2 nm.

For the intercalation/chemical stripping method, the organometallic nanoparticles obtained by mechanical peeling are usually small in size, larger in thickness, and less efficient (<15%). Therefore, the experimental method has been improved on this basis. Recently, Ding et al. [17] inserted the ligands containing disulfide bonds into layered MOFs by coordination insertion and then realized the efficient peeling of layered MOFs through the fracture of disulfide bonds, and to a certain extent, it can regulate the fracture process of disulfide bonds to achieve controllable preparation of organometallic nanoparticles (Figure 1.1). They cleverly use bipyridine ligands containing disulfide bonds to obtain MOFs, with increased inter-layer spacing through the intercalation of pyridine ligands, and then regu-late the interlaminar interaction of layered structures through the chemical reduction and fracture process of disulfide bonds, thus realizing the effi-cient chemical stripping of layered MOFs to obtain ultra-thin organome-tallic nanoparticles.

In addition, the above methods of synthesizing 2D metal-organic frame are bottom-up synthesis. Zn (bim) (OAc) MOFs ultra-thin nanoparticles were synthesized from the bottom up with a thickness of 5 nm. The yield of this technique can reach 65% by an intercalation/chemical stripping

Layered MOF Crystals Intercalated MOF Crystals 2D MOF Nanosheets

disul�de ligand

breakage

exfoliation

trimethylphosphine

intercalation

4,4’-dipyridyl disul�de

Figure 1.1 Schematic illustration of the overall process developed to produce 2D MOF nanosheets via an intercalation and chemical exfoliation approach [reprinted with permission from ref. 17. Copyright 2017 American Chemical Society].


method [22], the metal organic nanoparticles with 1-nm thickness can be prepared efficiently (~57%) by stirring at room temperature. At the same time, different thickness organometallic nanoparticles can be further obtained by controlling the reduction process of disulfide bonds in disul-fide ligands. Considering the large number of organic ligands and metal ions/clusters available in MOFs synthesis materials, the method reported in this paper was used to prepare 2D metal organic nanoparticles with dif-ferent structure and properties. This thickness controllable intercalation/ chemical stripping method has a broad prospect in the preparation of ultra-thin metal organic nanoparticles, and this preparation method pro-vides another different method for the controllable preparation of 2D nanomaterials.

1.2.7 Microwave Synthesis Method

Microwave is the electromagnetic wave, whose frequency is 300 Hz~ 300 GHz and the wavelength is between 1 mm to l m. It has longer wave-length and better penetration than infrared, far infrared, and other electro-magnetic waves used for radiation heating because microwave can transfer energy through molecular dipole rotation and ion conduction to heat the material. Therefore, in the process of microwave heating, the molecules will vibrate violently and rub with each other and raise the temperature [23]. The internal and external heating of the material is almost at the same time, which makes microwave heating have the advantages of fast heat-ing rate, high energy utilization rate, and no pollution to the environment compared with the traditional heating method. It has attracted extensive attention in the field of material synthesis.

Gordon et al. [24] synthesized MIL-53 (Fe) crystal used FeCl2.6H2O and H2BDC as raw materials by traditional heating method and micro-wave method. Scanning electron microscope analysis showed that the particle size of MIL-53 (Fe) crystal synthesized by microwave method is 1~5 μm, and the particle size distribution of MIL-53 (Fe) crystal synthe-sized by traditional heating method is 5-25 µm. The particle size distri-bution of MIL-53 (Fe) crystal synthesized by traditional heating method is 5-25 µm.

Microwave heating can realize rapid and uniform heating, so that the reactants can be mixed and uniform in a short period of time, so that the nucleus can crystallization rapidly, and the smaller particles and crystals with uniform size can be obtained by rapid crystallization.


1.2.8 Self-Assembly

Sun et al. [25] introduced a highly c-oriented NH2-MIL-125(Ti) Membranes by In-Plane Epitaxial Growth route, as shown as Figure 1.2. By using the method of dynamic gas-liquid interface self-assembly, the highly oriented monolayer of seeds can be obtained by orientation depo-sition of seeds. The controlled epitaxial growth process was realized by using single mode microwave reactor and transition metal sulfide TiS2 as titanium source in the secondary growth process. C-axis oriented NH2-MIL-125 (Ti) thin films were prepared by combining seed orientation deposition and controllable epitaxial secondary growth. The film has excellent gas separation performance. The ideal separation coefficient of H2/CO2 is 24.8 at 30°C and 1 bar, which is much higher than that of Nusen diffusion coefficient.

1.2.9 Special Interface Synthesis Method

Special interface synthesis method was used to assist the growth of 2D MOFs nanoparticles at some special interfaces (gas-liquid interface or liquid-liquid interface). For example, Kambe et al. [26] demonstrated a single-layer or multi-layer nickel dithiopentyl ring nanoparticles named nano-1. They use nickel acetate and phenylhexathiol as ions and ligands to facilitate the reaction of liquid-gas contact surface to form 2D MOF

Dynamic air-liquid interface-assisted assembly

Oriented membrane Single-mode microwave field

Oriented deposition

Secondary growth

Oriented seeding layerDI water flow

Figure 1.2 Schematic illustration of the preparation procedure of highly c-oriented NH2-MIL-125 (Ti) membrane by combining oriented seeding and controlled inplane secondary growth (Red sphere: Ti+4 ion, black rod: NH2-BDC) [reprinted with permission from ref. 25. Copyright 2018 Wiley].


materials. The thin layer containing benzene hexamercaptan was spread on the surface of aqueous solution containing Ni(OAc)2 and NaBr. After evaporation of ethyl acetate, the nano-1 nanoparticles will be formed at the liquid-gas interface and then they will be transferred to pyrolysis graphite with high crystallization orientation. Rodenas et al. [27] exhibited a three-layer synthesis strategy to synthesize CuBDC nanoparticles. The mixture of DMF and acetonitrile was arranged vertically into three layers to prepare other reaction systems. At the top of layer was the acetonitrile solution that dissolves copper nitrate, and the bottom layer was the DMF solution that dissolves terephthalic acid. The two layers use a mixture of the same amount of DMF and acetonitrile as the transition layer. When the ions in the upper layer and the ligands in the lower layer slowly spread to the inter-mediate layer, ultra-thin CuBDC nanoparticles appeared. Importantly, this three-layer synthesis method is commonly used and can be extended to synthesize 2D MOFs nanoparticles coordinated by other metal nodes and ligands.

1.2.10 Surfactant-Assisted Synthesis Method

Surfactant assisted method is also an effective method to generate 2D MOFs materials. The addition of surfactants not only limits the growth of MOFs along the vertical direction but also helps to disperse the synthesized MOFs nanoparticles. For example, Zhao et al. [12] found that the Zn-TCPP MOF coordinated by zinc ions and TCPP (4-(4- Carboxylphenyl) porphyrin) can obtain a 2D lamellar chopped bulk MOFs. It is formed by the connection of one Zn2(COO)4 water wheel metal node with four TCPP ligands. PVP can selectively stick to the outer sphere of MOFs, stabilize the existence of Zn-TCPP nanoparti-cles and limit its growth along the vertical direction, and promote the formation of ultra-thin Zn-TCPP nanoparticles. Ultra-thin Zn-TCPP nanoparticles can be obtained when a certain amount of polyvinylpyr-rolidone (PVP) was added.

1.2.11 Ultrasonic Synthesis

Ultrasonic synthesis is a new comprehensive subject which intersects chemistry and acoustics that belongs to the frontier subject in chemical synthesis [28]. As a special way of inputting energy the high efficiency of ultrasonic wave plays a difficult role in material synthesis by other methods such as light, electricity, heat, and so on. Ultrasonic chemistry can improve

layered 2d advanced materials - download.e-bookshelf.de · this edition first published 2020 by...

Documents