Graphene: Synthesis, Properties, and Phenomena

S ince its discovery in 2004, graphene has been a great sensation due to its unique structure and unusual properties, and it has only taken 6 years for a Noble Prize to be awarded for the field of graphene research. This monograph gives a well–balanced overview on all areas of scientific interest surrounding this fascinating nanocarbon. In one handy volume it offers comprehensive coverage of the topic, including chemical, materials science, nanoscience, physics, engineering, life science, and potential applications. Other graphene–like, inorganic layered materials are also discussed. Edited by two highly honored scientists, this is an invaluable companion for inorganic, organic, and physical chemists, materials scientists, and physicists.

Preface XIII List of Contributors XV 1 Synthesis, Characterization, and Selected Properties of Graphene 1 C. N. R. Rao, Urmimala Maitra, and H. S. S. Ramakrishna Matte 1.1 Introduction 1 1.2 Synthesis of Single–Layer and Few–Layered Graphenes 4 1.3 Synthesis of Graphene Nanoribbons 12 1.4 Selected Properties 15 1.5 Inorganic Graphene Analogs 39 References 40 2 Understanding Graphene via Raman Scattering 49 A. K. Sood and Biswanath Chakraborty 2.1 Introduction 49 2.2 Atomic Structure and Electronic Structure of Graphene 49 2.3 Phonons and Raman Modes in Graphene 51 2.4 Layer Dependence of Raman Spectra 57 2.5 Phonon Renormalization Due to Electron and Hole Doping of Graphene 61 2.6 Raman Spectroscopy of Graphene Edges and Graphene Nanoribbons 70 2.7 Effect of Disorder on the Raman Spectrum of Graphene 74 2.8 Raman Spectroscopy of Graphene under Strain 77 2.9 Temperature and Pressure Dependence of Raman Modes in Graphene as Nanometrological Tools 83 2.10 Tip–Enhanced Raman Spectroscopy of Graphene Layers 85 2.11 Conclusions 86 Acknowledgments 87 References 87 3 Physics of Quanta and Quantum Fields in Graphene 91 Ganapathy Baskaran 3.1 Introduction 91 3.2 Dirac Theory in 3 + 1 Dimensions: A Review 93 3.3 Band Structure of Graphene: Massless Chiral Dirac Electrons in 2 + 1 Dimensions 95 3.4 Anomaly – A Brief Introduction 100 3.5 Graphene and 2 + 1–Dimensional Parity Anomaly 105 3.6 Zitterbewegung 107 3.7 Klein Paradox 110 3.8 Relativistic–Type Effects and Vacuum Collapse in Graphene in Crossed Electric and Magnetic Fields 111 3.9 Prediction of Spin–1 Quanta from Resonating Valence Bond Correlations 116 3.10 Majorana Zero Mode from Two–Channel Kondo Effect in Graphene 120 3.11 Lattice Deformation as Gauge Fields 125 3.12 Summary 127 Acknowledgment 127 References 127 4 Magnetism of Nanographene 131 Toshiaki Enoki 4.1 Introduction 131 4.2 Theoretical Background of Magnetism in Nanographene and Graphene Edges 134 4.3 Experimental Approach to Magnetism of Nanographene 139 4.4 Magnetic Phenomena Arising in the Interaction with Guest Molecules in Nanographene–Based Nanoporous Carbon 146 4.5 Summary 154 Acknowledgment 155 References 155 5 Physics of Electrical Noise in Graphene 159 Vidya Kochat, Srijit Goswami, Atindra Nath Pal, and Arindam Ghosh 5.1 Introduction 159 5.2 Flicker Noise or ‘‘1/ f ’’ Noise in Electrical Conductivity of Graphene 169 5.3 Noise in Quantum Transport in Graphene at Low Temperature 179 5.4 Quantum–Confined Graphene 188 5.5 Conclusions and Outlook 193 References 193 6 Suspended Graphene Devices for Nanoelectromechanics and for the Study of Quantum Hall Effect 197 Vibhor Singh and Mandar M. Deshmukh 6.1 Introduction 197 6.2 Quantum Hall Effect in Graphene 198 6.3 Fabrication of Suspended Graphene Devices 200 6.4 Nanoelectromechanics Using Suspended Graphene Devices 201 6.5 Using Suspended Graphene NEMS Devices to Measure Thermal Expansion of Graphene 203 6.6 High–Mobility Suspended Graphene Devices to Study Quantum Hall Effect 206 Acknowledgments 208 References 208 7 Electronic and Magnetic Properties of Patterned Nanoribbons: A Detailed Computational Study 211 Biplab Sanyal 7.1 Introduction 211 7.2 Experimental Results 212 7.3 Theory of GNRs 214 7.4 Hydrogenation at the Edges 219 7.5 Novel Properties 226 7.6 Outlook 231 Acknowledgements 231 References 231 8 Stone–Wales Defects in Graphene and Related Two–Dimensional Nanomaterials 235 Sharmila N. Shirodkar and Umesh V. Waghmare 8.1 Introduction 235 8.2 Computational Methods 236 8.3 Graphene: Stone–Wales (SW) Defects 237 8.4 C1− x (BN) x / 2: C–BN Interfaces 255 8.5 Two–Dimensional MoS2 and MoSe2 259 8.6 Summary 265 Acknowledgments 266 References 266 9 Graphene and Graphene–Oxide–Based Materials for Electrochemical Energy Systems 269 Ganganahalli Kotturappa Ramesha and Srinivasan Sampath 9.1 Introduction 269 9.2 Graphene–Based Materials for Fuel Cells 270 9.3 Graphene–Based Supercapacitors 280 9.4 Graphene in Batteries 289 9.5 Conclusions and Future Perspectives 296 References 297 10 Heterogeneous Catalysis by Metal Nanoparticles Supported on Graphene 303 M. Samy El–Shall 10.1 Introduction 303 10.2 Synthesis of Graphene and Metal Nanoparticles Supported on Graphene 304 10.3 Pd/Graphene Heterogeneous Catalysts for Carbon–Carbon Cross–Coupling Reactions 319 10.4 CO Oxidation by Transition–Metal/Metal–Oxide Nanoparticles Supported on Graphene 330 10.5 Conclusions and Outlook 334 Acknowledgment 335 References 335 11 Graphenes in Supramolecular Gels and in Biological Systems 339 Santanu Bhattacharya and Suman K. Samanta 11.1 Introduction 339 11.2 Toward the Gelation of GO 341 11.3 Polymer–Assisted Formation of Multifunctional Graphene Gels 350 11.4 Graphene Aerogels 356 11.5 Hydrogel and Organogel as the Host for the Incorporation of Graphene 358 11.6 Biological Applications Involving Graphene 360 11.7 Conclusions and Future Directions 368 References 370 12 Biomedical Applications of Graphene: Opportunities and Challenges 373 Manzoor Koyakutty, Abhilash Sasidharan, and Shantikumar Nair 12.1 Introduction 373 12.2 Summary of Physical and Chemical Properties of Graphene 374 12.3 Cellular Uptake, Biodistribution, and Clearance 376 12.4 Toxicity of Graphene 379 12.5 Mitigation of Toxicity by Surface Modifications 390 12.6 In vivo Toxicity 391 12.7 Potential Application Areas: Opportunities 395 12.8 Conclusions 404 References 405 Index 409

C.N.R. Rao obtained his Ph.D. from Purdue University and D.Sc. from Mysore University as well as 53 honorary doctorate degrees from various universities. C.N.R. Rao is National Research Professor & Linus Pauling Research Professor at Jawaharlal Nehru Centre for Advanced Scientific Research and Honorary Professor at the Indian Institute of Science. His main research interests are in solid state and materials chemistry including nanomaterials. He is a member of numerous science academies worldwide and has received many national and international honors. In particular, he is the recipient of the Dan David Prize as well as the Illy Trieste Science Prize for Materials research besides the August von Wilhelm Hoffmann medal from the German Chemical Society. He has published over 1400 research papers and 45 books. A.K. Sood is Professor in the Department of Physics at the Indian Institute of Science, Bangalore. He holds the prestigious Bhatnagar Chair of CSIR and is currently the President of the Indian Academy of Sciences. His research interests include physics of nano–systems like nanotubes and graphene and physics of soft condensed matter. He has published more than 300 papers in refereed international journals and holds a few international patents. His work has been recognized by way of many honors and awards. These include Fellowships of The Indian National Science Academy, The National Academy of Sciences, India and The World Academy of Sciences (TWAS), Shanti Swaroop Bhatnagar Prize and National Award in Nanoscience and Nanotechnology by The Department of Science and Technology of India.

“This book will be useful to students, teachers, and researchers in material science interested in learning about and taking part in the exciting developments based on graphene.”  ( IEEE Electrical Insulation Magazine , 1 January 2014)