John Wiley & Sons Graphene Oxide Cover Due to its unique properties, graphene oxide has become one of the most studied materials of the las.. Product #: 978-1-119-06940-9 Regular price: $144.86 $144.86 Auf Lager

Graphene Oxide

Fundamentals and Applications

Dimiev, Ayrat M. / Eigler, Siegfied (eds.)

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1. Auflage November 2016
464 Seiten, Hardcover
Wiley & Sons Ltd
Dimiev, Ayrat M. / Eigler, Siegfied (Herausgeber)

ISBN: 978-1-119-06940-9
John Wiley & Sons

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Due 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 biomedical applications. In each case the differences and advantages of graphene oxide over its non-oxidised counterpart are discussed. The book concludes with a chapter on the challenges of industrial-scale graphene oxide production.

Graphene Oxide: Fundamentals and Applications is a valuable reference for academic researchers, and industry scientists interested in graphene oxide, graphene and other carbon materials.

About 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 H2 SO4 ?-GIC Graphite Intercalation Compound 42

2.4.3 Step 2: Transformation of Stage?-1 H2 SO4 ?-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
Dr. Ayrat M. Dimiev, EMD Performance Materials, Darmstadt, Germany.
Since 2009, Dr Dimiev has been working very closely with graphene oxide and other graphitic carbon nanomaterials. He spent five years at Rice University studying fundamental aspects of graphene oxide, resulting in several ground-breaking papers in highly ranked journals including Nature and Science, followed by a period at AZ Electronic Materials where he worked on optimizing mass production of graphene oxide, and on developing novel graphene oxide applications. Dr Dimiev currently works at EMD Performance Materials, a business of Merck KGaA, in Darmstadt, Germany.

Dr. Siegfried Eigler, Chalmers University of Technology, Department of Chemistry and Chemical Engineering, Göteborg, Sweden
Dr Eigler received his PhD in organic chemistry from the Friedrich-Alexander-Universit t Erlangen-Nürnberg in 2006 under the guidance of apl. Prof. Dr. Norbert Jux. Subsequently he conducted basic research on electrically conductive polymers and graphene oxide as an industry chemist. In 2011 he became a lecturer and research associate at the Friedrich-Alexander-Universität Erlangen-Nürnberg, where he did habilitation and in 2016 he became Associate Professor at the Chalmers University of Technology. His research focuses on the controlled chemistry of graphene.