List of Contributors xi
Series Preface xiii
Preface xv
1 Properties of Carbon Bulk Materials: Graphite and Diamond1Kamatchi Jothiramalingam Sankaran and Ken Haenen
1.1 Introduction 1
1.2 Graphite 2
1.2.1 History 2
1.2.2 sp2 Hybridization 3
1.2.3 Structure of Graphite 3
1.2.3.1 Hexagonal Graphite 3
1.2.3.2 Rhombohedral Graphite 3
1.2.3.3 Polycrystalline Graphite 4
1.2.3.4 Crystallite Imperfections 5
1.2.4 Natural and Synthetic Graphite 5
1.2.4.1 Natural Graphite 5
1.2.4.2 Synthetic Graphite 6
1.3 Diamond 7
1.3.1 History 7
1.3.2 sp3 Hybridization 8
1.3.3 Structure of Diamond 9
1.3.3.1 Crystal Forms of Diamond 9
1.3.4 Impurities in Diamond 10
1.3.4.1 Lattice Impurities 11
1.3.4.2 Inclusions 11
1.3.5 Natural and Synthetic Diamond 11
1.3.5.1 Natural Diamond 11
1.3.5.2 Synthetic Diamond 12
1.4 Characterization of Graphite and Diamond 14
1.4.1 Raman Spectroscopy 14
1.4.2 X-ray Diffraction 15
1.4.3 Electron Energy Loss Spectroscopy 15
1.4.4 X-ray Photoelectron Spectroscopy 17
1.4.5 Scanning Electron Microscopy 17
1.4.6 Transmission Electron Microscopy 17
1.5 Properties of Graphite and Diamond 18
1.6 Applications of Graphite and Diamond 20
1.6.1 Graphite 20
1.6.2 Diamond 20
References 21
2 Endohedral and Exohedral Single-Layered Fullerenes25Diana M. Bobrowska and Marta E. Plonska-Brzezinska
2.1 Introduction 25
2.2 Structure and Physicochemical Properties of Empty Single-Layered Fullerenes 25
2.3 Structure and Physicochemical Properties of Endohedral Fullerenes 29
2.4 Functionalization and Application of Single-Layered Fullerenes 32
2.4.1 Functionalization and Application of Exohedral Fullerenes 32
2.4.2 Functionalization and Application of Endohedral Metallofullerenes 38
2.5 Summary 42
Acknowledgments 42
References 42
3 Spherical Onion-Like Carbons63Diana M. Bobrowska and Marta E. Plonska-Brzezinska
3.1 Introduction 63
3.2 Structure of Onion-Like Carbons and Their Physicochemical Properties 63
3.3 Covalent and Noncovalent Functionalization of OLCs 69
3.4 Doping of OLCs by Heteroatoms 82
3.5 Applications of OLCs 84
3.5.1 Bioimaging 84
3.5.2 (Bio)Sensors 85
3.5.3 Energy Storage Devices 86
3.5.4 Solar Cells 88
3.5.5 Electronic and Photonic Applications 88
3.5.6 Sorbents 89
3.5.7 Catalysis and Electrocatalysis 89
3.5.8 Tribology 90
3.6 Summary 90
Acknowledgments 91
References 91
4 Carbon Nanotubes: Synthesis, Properties, and New Developments in Research107Marianna V. Kharlamova and Dominik Eder
4.1 Introduction 107
4.2 Atomic Structure of Carbon Nanotubes 108
4.3 Properties of Carbon Nanotubes 109
4.3.1 Electronic Properties 109
4.3.2 Mechanical Properties 110
4.3.3 Thermal Properties 111
4.4 Synthesis of Carbon Nanotubes 111
4.4.1 Arc-Discharge 111
4.4.2 Laser Ablation 112
4.4.3 Molten Salt Route/Electrolytic Process 113
4.4.4 Chemical Vapor Deposition 113
4.5 Postsynthesis Treatments of Carbon Nanotubes 114
4.5.1 Purification 114
4.5.2 Separation of Metallic and Semiconducting SWCNTs 115
4.5.3 Functionalization 116
4.6 New Developments in Carbon Nanotube Research: Toward Controllable Properties of Nanotubes 117
4.6.1 Chirality Selective Synthesis of SWCNTs 117
4.6.2 Chirality Selective Separation of SWCNTs 120
4.6.3 Substitutional Doping of SWCNTs 122
4.6.4 Exohedral Modification of CNTs: Nanotube Hybrids 123
4.6.5 Filling of SWCNT Interior Channels 124
4.7 Conclusions and Outlook 125
Acknowledgments 128
References 129
5 CNT Fiber-Based Hybrids: Synthesis, Characterization, and Applications in Energy Management149Moumita Rana, Cleis Santos, Alfonso Monreal-Bernal and Juan J. Vilatela
5.1 Introduction: What are CNT Fibers andWhy Do they Form Interesting Hybrids and Composites? 149
5.1.1 CNT Fiber Structure and Properties 149
5.1.2 Design Principles in CNT Fiber Hybrids 152
5.2 Hybridization with Metal Oxides 153
5.2.1 Surface Chemistry and Functionalization 154
5.2.2 Examples of Common Architectures: Layered, Particulates, Conformal 156
5.2.2.1 Particulate Systems 156
5.2.2.2 Layered Systems 161
5.2.2.3 Conformal CNT Fiber Hybrids 162
5.2.3 Hybrid Structure and Interfacial Characterization 163
5.2.3.1 Determination of Mass Fraction 163
5.2.3.2 Wetting and Interaction with Solvents 166
5.2.3.3 Specific Surface Area and Pore Size 168
5.2.4 Solid-State Transport Characterization of Layered Hybrids 169
5.2.4.1 Junction Characterization in Layered Hybrids 171
5.2.5 Interfacial Studies by Electrochemical Impedance Spectroscopy Methods 175
5.2.6 Advanced Interfacial Studies in ALD-Hybrid Test Systems 177
5.2.6.1 Residual Strain 177
5.2.6.2 Evidence of an Interfacial TiOC Bond 179
5.2.6.3 Electronic Structure of the TiOC Interface 180
5.3 EDLC Introducing Pseudocapacitive Reactions 182
5.4 Capacitive Deionization 185
5.5 Battery Electrodes 189
5.6 Conclusions and Perspective 193
References 194
6 Advanced Materials Designed with Nanodiamonds: Synthesis and Applications201Jean-Charles Arnault
6.1 Introduction 201
6.2 Synthesis of Isolated Objects from ND 203
6.2.1 ND Grafted with Molecules 203
6.2.1.1 Electrostatic Grafting 203
6.2.1.2 Chemical Grafting 206
6.2.2 Nanodiamonds as Templates 209
6.2.2.1 Decoration by Atoms or Clusters 209
6.2.2.2 Core Shells with Diamond Core 212
6.3 Decoration of Particles by ND, Core Shells with Diamond Shell 215
6.3.1 Nanodiamonds to Decorate or to Graft to NP 215
6.3.1.1 Emulsion 215
6.3.1.2 Decoration of Nanoparticles with ND 216
6.3.1.3 Decoration of Carbon Nanostructures by ND 217
6.3.2 Silica/Diamond Core Shells 218
6.4 Conclusion and Perspectives 219
References 220
7 Chemical Functionalization of Nanodiamond for Nanobiomedicine229Naoki Komatsu
7.1 Introduction 229
7.2 ND for Fluorescent Cell Labeling 229
7.2.1 Fluorophore-Immobilized ND 229
7.2.1.1 Synthesis 229
7.2.1.2 Cell Labeling 231
7.2.2 ND with Intrinsic Fluorescence 232
7.2.2.1 Synthesis 232
7.2.2.2 Cell Labeling 233
7.3 ND for MRI 235
7.3.1 Synthesis 235
7.3.2 MRI Relaxivity 238
7.4 ND for Gene Delivery 238
7.4.1 Synthesis 238
7.4.2 Gene Delivery 239
7.5 ND for Drug Delivery 241
7.5.1 Synthesis 241
7.5.2 Drug Delivery 243
7.6 Concluding Remarks 244
Acknowledgments 245
References 245
8 Nanocarbon Aerogels and Aerographite247Hubert Beisch and Bodo Fiedler
8.1 Introduction 247
8.2 Fabrication 247
8.2.1 Non-template Based and Template Based Methods 248
8.2.1.1 Non-template Based Synthesis 248
8.2.1.2 Template Based Synthesis 249
8.2.2 Template Based Synthesis of Aerographite and Globugraphite 249
8.2.2.1 Fabrication of Porous Ceramic Templates 249
8.2.2.2 CVD Synthesis 250
8.3 Morphology 253
8.3.1 Tetrapodal Networks 253
8.3.2 Globular Foam Structures with Hierarchical Pore Morphology 254
8.3.3 ReticularMorphology 255
8.3.4 Carbon Hybrids 256
8.4 Properties 258
8.4.1 Density 258
8.4.2 Electrical and Electrochemical Properties 259
8.4.2.1 Electrical Conductivity 259
8.4.2.2 Electrochemical Performance 262
8.5 Modifications 267
8.5.1 Metal and Metal Oxide Hybrids 267
8.5.2 Thermal Treatment (Annealing) 267
8.6 Conclusion 270
8.6.1 Summary 270
8.6.2 Outlook 271
References 271
9 Optoelectronic Properties of Nanocarbons and Nanocarbon Films275Cameron J. Shearer, LePing Yu and Joseph G. Shapter
9.1 Introduction 275
9.2 Nanocarbons 276
9.2.1 Graphene and Derivatives 276
9.2.1.1 Pristine Graphene via Micromechanical Exfoliation 276
9.2.1.2 Reduced Graphene/Graphite Oxide 278
9.2.1.3 Graphene from Chemical Vapor Deposition 278
9.2.2 Carbon Nanotubes 279
9.2.2.1 SWCNT Chirality 280
9.3 Fundamentals of Optical and Electronic Properties of Nanocarbons 280
9.3.1 Electronic Properties 280
9.3.1.1 Graphene 280
9.3.1.2 Carbon Nanotubes 282
9.3.2 Optical Properties 284
9.3.2.1 Graphene 284
9.3.2.2 Carbon Nanotubes 284
9.4 Optoelectronic Properties of Nanocarbon Films 287
9.4.1 The Figure of Merit (FOM) of Optoelectronic Devices 287
9.4.2 Techniques to Maximize FOM 287
9.5 Summary and Outlook 289
References 290
Index 295
