Description
Book SynopsisDue to its unique properties, graphene oxide has become one of the most studied materials of the last decade and a great variety of applications have been reported in areas such as sensors, catalysis and biomedical applications.
This comprehensive volume systematically describes the fundamental aspects and applications of graphene oxide. The book is designed as an introduction to the topic, so each chapter begins with a discussion on fundamental concepts, then proceeds to review and summarize recent advances in the field. Divided into two parts, the first part covers fundamental aspects of graphene oxide and includes chapters on formation and chemical structure, characterization methods, reduction methods, rheology and optical properties of graphene oxide solutions. Part Two covers numerous graphene oxide applications including field effect transistors, transparent conductive films, sensors, energy harvesting and storage, membranes, composite materials, catalysis and biomed
Table of ContentsAbout the Editors xi
List of Contributors xiii
Foreword xv
Preface xvi
Part I Fundamentals 1
1 Graphite Oxide Story – From the Beginning Till the Graphene Hype 3
Anton Lerf
1.1 Introduction 3
1.2 Preparation of Graphite Oxide 5
1.2.1 Trials for Improving and Simplifying GO Preparation 5
1.2.2 Over‐Oxidation of Graphite 8
1.2.3 Formation Mechanism – First Approximation 9
1.3 Discovery of Essential Functional O‐Containing Groups and its Relation to the Development of Structural Models 10
1.3.1 Analytical Composition of Graphite Oxide 10
1.3.2 Creation of the Structural Model from 1930 till 2006 11
1.3.3 Considerations for the Formation Mechanism – Second Approximation 16
1.4 Properties of Graphite Oxide 18
1.4.1 Thermal Degradation and its Products 18
1.4.2 Chemical Reduction Reactions 19
1.4.3 Reactions with Acids and Bases 21
1.4.4 “Osmotic Swelling”: Hydration Behavior and Colloid Formation 22
1.4.5 GO Acidity 23
1.4.6 Intercalation and Functionalization Reactions 26
1.4.7 Functional Groups, their Reactions and their Relation to GO Formation and Destruction 28
1.5 Epilogue 29
References 30
2 Mechanism of Formation and Chemical Structure of Graphene Oxide 36
Ayrat M. Dimiev
2.1 Introduction 36
2.2 Basic Concepts of Structure 37
2.3 Preparation Methods 39
2.4 Mechanism of Formation 41
2.4.1 Theoretical Studies and System Complexity 41
2.4.2 Step 1: Formation of Stage‐1 H 2 So 4 ‐GIC Graphite Intercalation Compound 42
2.4.3 Step 2: Transformation of Stage‐1 H 2 So 4 ‐ GIC to Pristine Graphite Oxide 43
2.4.4 Pristine Graphite Oxide Structure 45
2.4.5 Step 3: Delamination of Pristine Graphite Oxide 47
2.5 Transformation of Pristine Graphite Oxide Chemical Structure Upon Exposure to Water 47
2.6 Chemical Structure and Origin of Acidity 51
2.6.1 Structural Models and the Actual Structure 51
2.6.2 Origin of Acidity and the Dynamic Structural Model 57
2.7 Density of Defects and Introduction of Oxo‐Functionalized Graphene 64
2.7.1 Oxo‐Functionalized Graphene by Charpy–Hummers Approach 65
2.7.2 Oxo‐Functionalized Graphene from Graphite Sulfate 69
2.8 Addressing the Challenges of the Two‐Component Structural Model 72
2.9 Structure of Bulk Graphite Oxide 76
2.10 Concluding Remarks 80
References 81
3 Characterization Techniques 85
Siegfried Eigler and Ayrat M. Dimiev
3.1 Nuclear Magnetic Resonance Spectroscopy of Graphene Oxide 85
3.1.1 Nuclear Magnetic Resonance Spectroscopy in Solids 85
3.1.2 Nuclear Magnetic Resonance Spectroscopy of Graphene Oxide 87
3.1.3 Discussion 92
3.2 Infrared Spectroscopy 93
3.3 X‐ray Photoelectron Spectroscopy 97
3.4 Raman Spectroscopy 100
3.4.1 Introduction 101
3.4.2 Raman Spectroscopy on Molecules 101
3.4.3 Raman Spectroscopy on Graphene, GO and RGO 101
3.4.4 Defects in Graphene 103
3.4.5 Raman Spectra of GO and RGO 104
3.4.6 Statistical Raman Microscopy (SRM) 109
3.4.7 Outlook 110
3.5 Microscopy Methods 111
3.5.1 Scanning Electron Microscopy 113
3.5.2 Atomic Force Microscopy 114
3.5.3 Transmission Electron Microscopy 115
3.5.4 High‐Resolution Transmission Electron Microscopy 115
References 118
4 Rheology of Graphene Oxide Dispersions 121
Cristina Vallés
4.1 Liquid Crystalline Behaviour of Graphene Oxide Dispersions 121
4.1.1 Liquid Crystals and Onsager’s Theory 121
4.1.2 Nematic Phases in Carbon Nanomaterials 122
4.2 Rheological Behaviour of Aqueous Dispersions of LC‐GO 124
4.2.1 Dynamic Shear Properties 125
4.2.2 Steady Shear Properties 128
4.2.3 Recovery of the Structure 133
4.2.4 Tuning the Rheology of GO Dispersions to Enable Fabrication 133
4.2.5 Electro‐Optical Switching of LC‐GO with an Extremely Large Kerr Coefficient 136
4.3 Comparison with Other Systems 138
4.3.1 Comparison of Aqueous and Polymer Matrix Systems 138
4.3.2 Comparison Between Aqueous Dispersions of GO and Oxidized Carbon Nanotubes: Role of Dimensionality 141
4.4 Summary and Perspectives 142
References 143
5 Optical Properties of Graphene Oxide 147
Anton V. Naumov
5.1 Introduction 147
5.2 Absorption 148
5.3 Raman Scattering 153
5.4 Photoluminescence 155
5.5 Graphene Oxide Quantum Dots 168
5.6 Applications 169
References 170
6 Functionalization and Reduction of Graphene Oxide 175
Siegfried Eigler and Ayrat M. Dimiev
6.1 Introduction 175
6.2 Diverse Structure of Graphene Oxide 176
6.3 Stability of Graphene Oxide 178
6.3.1 Thermal Stability of Graphene Oxide 178
6.3.2 Stability and Chemistry of Graphene Oxide in Aqueous Solution 179
6.3.3 Stability of Oxo‐Functionalized Graphene 182
6.4 Non‐Covalent Chemistry 184
6.5 Covalent Chemistry 186
6.5.1 Reactions Mainly at the Basal Plane 187
6.5.2 Consideration About C–C Bond Formation on the Basal Planes 192
6.5.3 Reactions at Edges 192
6.6 Reduction and Disproportionation of Graphene Oxide 200
6.6.1 Reduction 200
6.6.2 Disproportionation 203
6.6.3 Reduction Strategies 207
6.6.4 Reduction of Oxo‐Functionalized Graphene 209
6.7 Reactions with Reduced Form of Graphene Oxide 212
6.8 Controlled Chemistry with Graphene Oxide 215
6.8.1 Nomenclature of Polydisperse and Functionalized Graphene 215
6.8.2 Organosulfate in Graphene Oxide – Thermogravimetric Analysis 216
6.8.3 Synthetic Modifications of Oxo‐Functionalized Graphene 218
6.9 Discussion 223
References 224
Part II Applications 231
7 Field‐Effect Transistors, Sensors and Transparent Conductive Films 233
Samuele Porro and Ignazio Roppolo
7.1 Field‐Effect Transistors 233
7.2 Sensors 237
7.2.1 Gas Sensors 238
7.2.2 Humidity Sensors 240
7.2.3 Biological Sensors 240
7.3 RGO Transparent Conductive Films 243
7.4 Memristors Based on Graphene Oxide 245
7.4.1 Fabrication of Devices 246
7.4.2 Switching Mechanisms 248
References 250
8 Energy Harvesting and Storage 257
Cary Michael Hayner
8.1 Solar Cells 257
8.2 Lithium‐Ion Batteries 258
8.2.1 Introduction 258
8.2.2 Electrochemistry Fundamentals 258
8.2.3 Anode Applications 261
8.2.4 Cathode Applications 270
8.2.5 Emerging Applications 275
8.3 Supercapacitors 278
8.3.1 Introduction 278
8.3.2 Electrochemistry Fundamentals 279
8.3.3 Carbon‐only Electrodes 280
8.3.4 Pseudo‐Capacitive GO–Composite Electrodes 287
8.4 Outlook and Future Development Opportunities 291
References 292
9 Graphene Oxide Membrane for Molecular Separation 296
Ho Bum Park, Hee Wook Yoon and Young Hoon Cho
9.1 Rise of Graphene‐Based Membranes: Two Approaches 296
9.2 GO Membrane: Structural Point of View 298
9.3 GO Membrane for Gas Separation 299
9.4 GO Membrane for Water Purification and Desalination 305
9.5 Other Membrane Applications 309
9.5.1 Fuel Cell Membrane 309
9.5.2 Ion‐Selective Membrane for Next‐Generation Batteries 310
9.5.3 Dehydration 311
9.6 Conclusions and Future Prospects 311
References 312
10 Graphene Oxide‐Based Composite Materials 314
Mohsen Moazzami Gudarzi, Seyed Hamed Aboutalebi and Farhad Sharif
10.1 Introduction 314
10.1.1 How Graphite Met Polymers? 316
10.1.2 Graphite Oxide‐Based Composites 318
10.1.3 CNTs Versus Graphene (Oxide) 319
10.2 Why Mix Graphene Oxide and Polymers? 323
10.2.1 Making Stronger Polymers: Mechanical Properties 325
10.2.2 Electrical Properties 333
10.2.3 Thermal Conductivity 339
10.2.4 Barrier Properties 341
10.3. Graphene Oxide or Graphene Oxides? 344
10.3.1 Size Effect 344
10.3.2 Effect of Medium on GO Structure 347
10.3.3 The Purification Process 347
10.3.4 Thermal Instability 349
10.3.5 Health Issues 349
10.3.6 Environmental Impact 351
10.4 Conclusion 351
References 352
11 Toxicity Studies and Biomedical Applications of Graphene Oxide 364
Larisa Kovbasyuk and Andriy Mokhir
11.1 Introduction 364
11.2 Toxicity of Graphene Oxide 365
11.3 On the Toxicity Mechanism 366
11.3.1 Membrane as a Target 366
11.3.2 Oxidative Stress 368
11.3.3 Other Factors 369
11.4 Biomedical Applications of Graphene Oxide 370
11.4.1 Graphene Oxide in Treatment of Cancer and Bacterial Infections 370
11.4.2 Photothermal Therapy 370
11.4.3 Graphene Oxide as a Drug Carrier 371
11.5 Bioanalytical Applications 376
Acknowledgments 378
References 378
12 Catalysis 382
Ioannis V. Pavlidis
12.1 Introduction 382
12.2 Graphene Oxide Properties 383
12.3 Oxidative Activity 384
12.3.1 Oxidation Reactions of GO 384
12.3.2 Oxidation of Sulfur Compounds 391
12.3.3 Functionalized Materials 393
12.4 Polymerization 394
12.5 Oxygen Reduction Reaction 396
12.6 Friedel–Crafts and Michael Additions 399
12.7 Photocatalysis 400
12.8 Catalytic Activity of Other Layered Carbon‐Based Materials and Hybrid Materials of GO 400
12.8.1 Non‐Functionalized Carbon‐Based Nanomaterials 400
12.8.2 Hybrid Catalysts and Alternative Applications 401
12.9 Outlook 404
References 405
13 Challenges of Industrial‐Scale Graphene Oxide Production 410
Sean E. Lowe and Yu Lin Zhong
13.1 Introduction 410
13.2 Scope and Scale of the Graphene Market 411
13.3 Overview of Graphene Oxide Synthesis 414
13.4 Challenges of Graphene Oxide Production 416
13.4.1 Graphite Sources 416
13.4.2 Reaction Conditions 418
13.4.3 Work‐up and Purification 422
13.4.4 Storage, Handling and Quality Control 425
13.5 Concluding Remarks and Future Directions 427
References 428
Vocabulary 432
Index 435
