Meta-Nanotubes are a new generation of carbon nanotubes (CNTs) which result from the chemical transformation of regular CNTs and their subsequent combination with foreign materials (atoms, molecules, chemical groups, nanocrystals) by various ways such as functionalisation, doping, filling, and substitution. These new nanomaterials exhibit enhanced or new properties, such as reactivity, solubility, and magnetism, which pristine CNTs do not possess. Their many applications include electronic and optoelectronic devices, chemical and biosensors, solar cells, drug delivery, and reinforced glasses and ceramics.
Carbon Meta-Nanotubes: Synthesis, Properties and Applications discusses these third generation carbon nanotubes and the unique characteristics they possess. Beginning with a general overview of the subject, this book covers the five main categories of meta-nanotubes, namely:
Doped Carbon NanotubesFunctionalised Carbon NanotubesDecorated or Coated Carbon NanotubesFilled Carbon NanotubesHeterogeneous Nanotubes
Providing unparalleled coverage of these third generation or meta-nanotubes, and possibilities for future development, this book is essential for anyone working on carbon nanotubes.
List of Contributors xiiiForeword xv
List of Abbreviations xvii
Acknowledgements xxi
Introduction to the Meta-Nanotube Book 1
Marc Monthioux
1 Time for a Third-Generation of Carbon Nanotubes 1
2 Introducing Meta-Nanotubes 2
2.1 Doped Nanotubes (X:CNTs) 3
2.2 Functionalized Nanotubes (X-CNTs) 3
2.3 Decorated (Coated) Nanotubes (X /CNTs) 3
2.4 Filled Nanotubes (X@CNTs) 3
2.5 Heterogeneous Nanotubes (X*CNTs) 4
3 Introducing the Meta-Nanotube Book 4
References 5
1 Introduction to Carbon Nanotubes 7
Marc Monthioux
1.1 Introduction 7
1.2 One Word about Synthesizing Carbon Nanotubes 7
1.3 SWCNTs: The Perfect Structure 11
1.4 MWCNTs: The Amazing (Nano)Textural Variety 18
1.5 Electronic Structure 29
1.6 Some Properties of Carbon Nanotubes 31
1.7 Conclusion 36
References 36
2 Doped Carbon Nanotubes: (X:CNTs) 41
Alain Pénicaud, Pierre Petit and John E. Fischer
2.1 Introduction 41
2.1.1 Scope of this Chapter 41
2.1.2 A Few Definitions 42
2.1.3 Doped/Intercalated Carbon Allotropes a Brief History 43
2.1.4 What Happens upon Doping SWCNTs? 48
2.2 n-Doping of Nanotubes 52
2.2.1 Synthetic Routes for Preparing Doped SWCNTs 52
2.2.2 Crystalline Structure and Chemical
Composition of n-Doped Nanotubes 54
2.2.3 Modification of the Electronic Structure of SWCNTs upon Doping 59
2.2.4 Electrical Transport in Doped SWCNTs 61
2.2.5 Spectroscopic Evidence for n-Doping 65
2.2.6 Solutions of Reduced Nanotubes 72
2.3 p-Doping of Carbon Nanotubes 73
2.3.1 p-Doping of SWCNTs with Halogens 74
2.3.2 p-Doping with Acceptor Molecules 80
2.3.3 p-Doping of SWCNTs with FeCl3 84
2.3.4 p-Doping of SWCNTs with SOCl2 87
2.3.5 p-Doping of SWCNTs with Acids 87
2.3.6 p-Doping of SWCNTs with Superacids 91
2.3.7 p-Doping with other Oxidizing Agents 95
2.3.8 Diameter Selective Doping 96
2.4 Practical Applications of Doped Nanotubes 99
2.5 Conclusions, Perspectives 100
References 101
3 Functionalized Carbon Nanotubes (X-CNTs) 113
Stéphane Campidelli, Stanislaus S. Wong and Maurizio Prato
3.1 Introduction 113
3.2 Functionalization Routes 113
3.2.1 Noncovalent Sidewall Functionalization of SWCNTs 114
3.2.2 Covalent Functionalization of SWCNTs 114
3.3 Properties and Applications 125
3.3.1 Electron Transfer Properties and Photovoltaic Applications 125
3.3.2 Chemical Sensors (FET-Based) 137
3.3.3 Opto-Electronic Devices (FET-Based) 139
3.3.4 Biosensors 145
3.4 Conclusion 149
References 150
4 Decorated (Coated) Carbon Nanotubes (X/CNTs) 163
Revathi R. Bacsa and Philippe Serp
4.1 Introduction 163
4.2 Metal-Nanotube Interactions Theoretical Aspects 166
4.2.1 Curvature-Induced Effects 168
4.2.2 Effect of Defects and Vacancies on the Metal-Graphite Interactions 169
4.3 Carbon Nanotube Surface Activation 170
4.4 Methods for Carbon Nanotube Coating 171
4.4.1 Deposition from Solution 171
4.4.2 Self-Assembly Methods 178
4.4.3 Electro- and Electrophoretic Deposition 183
4.4.4 Deposition from Gas Phase 187
4.4.5 Nanoparticles Decorating Inner Surfaces of Carbon Nanotubes 190
4.5 Characterization of Decorated Nanotubes 191
4.5.1 Electron Microscopy and X-ray Diffraction 191
4.5.2 Spectroscopic Methods 192
4.5.3 Porosity and Surface Area 196
4.6 Applications of Decorated Nanotubes 196
4.6.1 Sensors 196
4.6.2 Catalysis 198
4.6.3 Fuel Cells 202
4.6.4 Hydrogen Storage 204
4.7 Decorated Nanotubes in Biology and Medicine 205
4.8 Conclusions and Perspectives 207
References 208
5 Filled Carbon Nanotubes 223
5.1 Presentation of Chapter 5 223
5a Filled Carbon Nanotubes: (X@CNTs) 225
Jeremy Sloan and Marc Monthioux
5a.1 Introduction 225
5a.2 Synthesis of X@CNTs 227
5a.2.1 A Glimpse at the Past 227
5a.2.2 The Expectations with Filling CNTs 228
5a.2.3 Filling Parameters, Routes and Mechanisms 229
5a.2.4 Materials for Filling 240
5a.2.5 Filling Mechanisms 245
5a.3 Behaviours and Properties 247
5a.3.1 Peculiar in-Tube Behaviour (Diffusion, Coalescence, Crystallization) 247
5a.3.2 Electronic Properties (Transport, Magnetism and Others) 252
5a.4 Applications (Demonstrated or Expected) 256
5a.4.1 Applications that Make Use of Mass
Transport Properties 256
5a.4.2 Applications Arising as a Result of Filling 258
Acknowledgements 261
References 261
5b Fullerenes inside Carbon Nanotubes: The Peapods 273
F. Simon and Marc Monthioux
5b.1 Introduction 273
5b.2 The Discovery of Fullerene Peapods 274
5b.3 Classification of Peapods 277
5b.4 Synthesis and Behavior of Fullerene Peapods 279
5b.4.1 Synthesis of Peapods 279
5b.4.2 Behavior of Peapods under Various Treatments 289
5b.5 Properties of Peapods 295
5b.5.1 Structural Properties 295
5b.5.2 Peapod Band Structure from Theory and Experiment 298
5b.5.3 Transport Properties 301
5b.5.4 Optical Properties 302
5b.5.5 Vibrational Properties 303
5b.5.6 Magnetic Properties 305
5b.6 Applications of Peapods 308
5b.6.1 Demonstrated Applications 308
5b.6.2 Expected Applications 310
Acknowledgements 314
References 314
6 Heterogeneous Nanotubes (X*CNTs, X*BNNTs) 323
Dmitri Golberg, Mauricio Terrones
6.1 Overall Introduction 323
6.2 Pure BN Nanotubes 324
6.2.1 Introduction 324
6.2.2 Synthesis of BN Nanotubes 325
6.2.3 Morphology and Structure of BN Nanotubes 331
6.2.4 Properties of BN Nanotubes 337
6.2.5 Stability of BN Nanotubes to High-Energy Irradiation 346
6.2.6 Boron Nitride Meta-Nanotubes 346
6.2.7 Other BN Nanomaterials 353
6.2.8 Challenging Applications 355
6.3 BxCyNz Nanotubes and Nanofibers 359
6.3.1 Tuning the Electronic Structure with C-Substituted BN Nanotubes 359
6.3.2 Production and Characterization of BxCyNz Nanotubes and Nanofibers 362
6.4 B-Substituted or N-Substituted Carbon Nanotubes 368
6.4.1 Substituting Carbon Nanotubes with B or N 368
6.4.2 Synthesis Strategies for Producing Bor N-Substituted CNTs 370
6.4.3 Morphology and Structure of Substituted CNTs 374
6.4.4 Properties of Substituted CNTs 379
6.4.5 Applications of Substituted CNTs 385
6.5 Perspectives and Future Outlook 392
Acknowledgements 394
References 395
Index
