Table Of Content

Graphene Oxide Graphene Oxide Fundamentals and Applications Edited by AyrAt M. DiMiEv Laboratory of Advanced Carbon Nanostructures, Kazan Federal University, Kazan, Russian Federation SiEgFriED EiglEr Department of Chemistry and Chemical Engineering, Chalmers University of Technology, Sweden this edition first published 2017 © 2017 John Wiley & Sons, ltd Registered Office John Wiley & Sons, ltd, the Atrium, Southern gate, Chichester, West Sussex, PO19 8SQ, United Kingdom For details of our global editorial offices, for customer services and for information about how to apply for permission to reuse the copyright material in this book please see our website at www.wiley.com. the right of the author to be identified as the author of this work has been asserted in accordance with the Copyright, Designs and Patents Act 1988. All rights reserved. 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Further, readers should be aware that internet Websites listed in this work may have changed or disappeared between when this work was written and when it is read. No warranty may be created or extended by any promotional statements for this work. Neither the publisher nor the author shall be liable for any damages arising herefrom. Library of Congress Cataloging‐in‐Publication Data Names: Dimiev, Ayrat M., 1965– | Eigler, Siegfried, 1978– title: graphene oxide : fundamentals and applications / Ayrat M. Dimiev, Siegfried Eigler. Description: Chichester, West Sussex : John Wiley & Sons, inc., 2017. | includes bibliographical references and index. identifiers: lCCN 2016018225| iSBN 9781119069409 (cloth) | iSBN 9781119069430 (epub) Subjects: lCSH: graphene. | graphene–Oxidation. | graphene–industrial applications. Classification: lCC tA455.g65 D56 2017 | DDC 662/.9–dc23 lC record available at https://lccn.loc.gov/2016018225 A catalogue record for this book is available from the British library. Set in 10/12pt times by SPi global, Pondicherry, india 10 9 8 7 6 5 4 3 2 1 Contents 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 vi Contents 2.4 Mechanism of Formation 41 2.4.1 Theoretical Studies and System Complexity 41 2.4.2 Step 1: Formation of Stage‐1 HSO‐GIC Graphite 2 4 Intercalation Compound 42 2.4.3 Step 2: Transformation of Stage‐1 HSO‐GIC 2 4 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 Contents vii 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 viii Contents 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 Contents ix 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 x Contents 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