Carbon Materials and Nanotechnology

Carbon Materials and Nanotechnology......Page 5
Contents......Page 7
Preface......Page 15
1.1 History......Page 17
1.2 Structure and Bonding......Page 22
1.2.1 Graphite and Its Structure......Page 23
1.2.2 Diamond and Its Structure......Page 25
1.2.3 Structure of Other Carbon Allotropes......Page 26
1.3.1 Graphite and Related Materials......Page 29
1.3.2 Diamond......Page 33
1.4 Physical Properties......Page 36
1.4.1 Graphite and Related Materials......Page 37
1.4.2 Diamond......Page 39
1.5 Chemical Properties......Page 40
1.5.1 Graphite and Related Materials......Page 42
1.6 Application and Perspectives......Page 45
1.6.3 Other Carbon Materials......Page 46
1.7 Summary......Page 47
2.1.1 Theoretical Predictions......Page 49
2.1.2 Experimental Proof......Page 50
2.2.1 Nomenclature......Page 52
2.2.2 The Structure of C60......Page 53
2.2.3 Structure of Higher Fullerenes and Growth Mechanisms......Page 56
2.2.4 Structure of Smaller Carbon Clusters......Page 61
2.2.5 Structure of Heterofullerenes......Page 62
2.3 Occurrence, Production, and Purification......Page 63
2.3.1 Fullerene Preparation by Pyrolysis of Hydrocarbons......Page 64
2.3.2 Partial Combustion of Hydrocarbons......Page 65
2.3.3 Arc Discharge Methods......Page 66
2.3.4 Production by Resistive Heating......Page 67
2.3.5 Rational Syntheses......Page 68
2.3.6 Enrichment and Purification......Page 70
2.3.7 Preparation of Heterofullerenes......Page 72
2.4.1.1 Solubility......Page 73
2.4.1.2 Spectroscopic Properties......Page 75
2.4.1.3 Thermodynamic Properties......Page 79
2.4.1.4 Solid C60......Page 80
2.4.2 Properties of Higher Fullerenes......Page 81
2.5 Chemical Properties......Page 82
2.5.1.1 Typical Reactions of Fullerenes......Page 83
2.5.1.3 Secondary and Multiple Additions......Page 84
2.5.2.1 Electrochemistry of Fullerenes......Page 88
2.5.2.2 Reductions of Fullerenes......Page 90
2.5.2.3 Oxidations of Fullerenes......Page 92
2.5.3 Inorganic Chemistry of Fullerenes......Page 93
2.5.4.1 Metallofullerenes......Page 98
2.5.4.2 Endohedral Compounds with Nonmetallic Elements......Page 102
2.5.5.1 Hydrogenation and Halogenation......Page 103
2.5.5.2 Nucleophilic Addition to Fullerenes......Page 109
2.5.5.3 Cycloadditions......Page 114
2.5.5.4 Photochemistry......Page 119
2.5.5.5 Radical Chemistry of Fullerenes......Page 121
2.5.5.6 Fullerenes in Polymeric Materials and on Surfaces......Page 123
2.5.6 Supramolecular Chemistry of Fullerenes......Page 128
2.5.7 Polymeric Fullerenes and Behavior under High Pressure......Page 132
2.5.8 Reactivity of Further Fullerenes......Page 133
2.6 Applications and Perspectives......Page 134
2.7 Summary......Page 137
3.1 Introduction......Page 139
3.2.1 Nomenclature......Page 142
3.2.2 Structure of Single-Walled Carbon Nanotubes......Page 143
3.2.3 Structure of Multiwalled Carbon Nanotubes......Page 151
3.3.1.1 Arc Discharge Methods......Page 156
3.3.1.2 Laser Ablation......Page 158
3.3.1.3 The HiPCo Process......Page 160
3.3.1.4 Pyrolysis......Page 162
3.3.1.5 Chemical Vapor Deposition (CVD)......Page 163
3.3.2.1 Arc Discharge Methods......Page 166
3.3.2.2 Laser Ablation......Page 169
3.3.2.3 Chemical Vapor Deposition (CVD)......Page 170
3.3.2.4 Decomposition of Hydrocarbons– Pyrolytic Methods......Page 172
3.3.2.5 Production of Double-Walled Carbon Nanotubes......Page 174
3.3.3 Strategies for the Rational Synthesis of Carbon Nanotubes......Page 175
3.3.4.1 Bamboo-Like Carbon Nanotubes......Page 179
3.3.4.2 Cup-Stacked Carbon Nanotubes......Page 180
3.3.4.3 Carbon Nanohorns (SWNH)......Page 181
3.3.4.4 Helical Carbon Nanotubes (hMWNT)......Page 182
3.3.5 Arrays of Carbon Nanotubes......Page 184
3.3.6.1 Removal of Impurities from Carbon Nanotube Materials......Page 187
3.3.6.2 Evaluating the Purity of Carbon Nanotube Materials......Page 189
3.3.6.3 Cutting of Carbon Nanotubes......Page 192
3.3.6.4 Separation of Carbon Nanotubes by their Properties......Page 193
3.3.7.1 Arc Discharge Methods......Page 196
3.3.7.2 CVD-Methods......Page 201
3.4.1 General Considerations......Page 202
3.4.2 Solubility and Debundling of Carbon Nanotubes......Page 203
3.4.3 Mechanical Properties of Carbon Nanotubes......Page 206
3.4.4.1 Band Structure and Density of States of Carbon Nanotubes......Page 210
3.4.4.2 The Mechanism of Electric Conduction in Carbon Nanotubes......Page 218
3.4.4.3 Field Emission from Carbon Nanotubes......Page 220
3.4.5.1 Raman and Infrared Spectroscopy of Carbon Nanotubes......Page 222
3.4.5.2 Absorption and Emission Spectroscopy of Carbon Nanotubes......Page 225
3.4.5.3 ESR-Spectroscopic Properties of Carbon Nanotubes......Page 228
3.4.5.4 Further Spectroscopic Properties of Carbon Nanotubes......Page 229
3.4.6.2 Heat Conductivity of Carbon Nanotubes......Page 232
3.5.1 General Considerations on the Reactivity of Carbon Nanotubes......Page 233
3.5.2 Redox Chemistry of Carbon Nanotubes......Page 236
3.5.3 Functionalization of the Caps or Open Ends of Carbon Nanotubes......Page 240
3.5.4.1 Covalent Attachment of the Functional Groups......Page 242
3.5.4.2 Noncovalent Attachment of Functional Units......Page 256
3.5.5 Composite Materials with Carbon Nanotubes......Page 262
3.5.5.1 Composites with Covalent Bonding of the Polymer......Page 264
3.5.5.2 Composites with Noncovalent Attachment of the Polymer......Page 265
3.5.5.3 Nanotube Composites with Different Polymers......Page 266
3.5.5.4 Nanotube Composites with Other Materials......Page 270
3.5.6 Intercalation Compounds and Endohedral Functionalization of Carbon Nanotubes......Page 271
3.5.7 Supramolecular Chemistry of Carbon Nanotubes......Page 279
3.6 Applications and Perspectives......Page 282
3.6.1.1 Nanotubes as Tips in Atomic Force Microscopy......Page 283
3.6.1.2 Field Emission......Page 284
3.6.1.3 Field Effect Transistors......Page 285
3.6.2.2 Chemical Sensors......Page 287
3.6.3.1 Recognition of DNA Sequences......Page 289
3.6.3.2 Delivery of Drugs and Vaccines; Gene Therapy......Page 290
3.6.4 Materials with Carbon Nanotubes......Page 291
3.6.5.1 Heterogeneous Catalysis......Page 293
3.6.5.2 Hydrogen Storage in Carbon Nanotubes......Page 294
3.6.5.3 Carbon Nanotubes as Material in Electrical Engineering......Page 295
3.7 Summary......Page 296
4.1 Introduction......Page 299
4.2.1 Structure of Carbon Onions......Page 300
4.2.2 Structure of Faceted Carbon Nanoparticles......Page 305
4.2.3 Occurrence of Carbon Onions and Nanoparticles......Page 306
4.3.1 Arc Discharge Methods......Page 307
4.3.2 CVD-Methods......Page 309
4.3.3 Preparation of Carbon Onions by Ion Bombardment......Page 310
4.3.4 Chemical Methods......Page 312
4.3.5.1 Thermal Transformations of Soot-Like Structures......Page 314
4.3.5.2 Irradiation of Soot-Like and Other sp2-Hybridized Carbons......Page 316
4.3.5.3 Thermal Transformation of Diamond......Page 319
4.3.5.4 Irradiation of Diamond Materials......Page 320
4.3.6 Further Methods to Produce Carbon Onions......Page 321
4.3.7.1 Growth Mechanisms of Carbon Onions Obtained by Electron Irradiation......Page 323
4.3.7.2 Growth Mechanisms of Carbon Onions Obtained by Thermal Treatment......Page 325
4.4.1 Spectroscopic Properties......Page 329
4.4.1.1 IR- and Raman Spectroscopy......Page 330
4.4.1.2 X-Ray Diffraction......Page 331
4.4.1.3 Absorption Spectra of Carbon Onions and Related Materials......Page 332
4.4.1.4 EEL-Spectra of Carbon Onions and Related Materials......Page 333
4.4.1.5 Further Spectroscopic Properties of Carbon Onions and Related Materials......Page 334
4.4.2 Thermodynamic Properties......Page 335
4.4.3 Electronic Properties......Page 336
4.5.1 Reactivity and Functionalization of Carbon Onions and Carbon Nanoparticles......Page 337
4.5.2 Conversion into Other Forms of Carbon......Page 339
4.6 Applications and Perspectives......Page 340
4.6.1 Tribological Applications......Page 341
4.6.2 Applications in Catalysis......Page 342
4.7 Summary......Page 343
5.1.1 Historical Background to the Discovery of Nanodiamonds......Page 345
5.1.2 Natural Occurrence of Nanodiamond......Page 347
5.2.1 The Lattice Structure of Nanodiamond......Page 348
5.2.2 The Surface Structure of Nanodiamond......Page 349
5.2.3 Diamond or Graphite? Stability in the Nanometer Range......Page 352
5.2.4 Agglomeration of Nanodiamond......Page 354
5.3.1 Detonation Synthesis......Page 356
5.3.2 Shock Syntheses of Nanodiamond......Page 360
5.3.3 Further Methods of Nanodiamond Preparation......Page 362
5.3.4 Deagglomeration and Purification......Page 365
5.4.1.1 Raman Spectroscopy......Page 367
5.4.1.2 Infrared Spectroscopy......Page 370
5.4.1.3 X-Ray Diffraction and EELS......Page 372
5.4.1.4 Absorption and Photoluminescence Spectroscopy......Page 374
5.4.1.5 Further Spectroscopic Properties......Page 376
5.4.2 Electronic Properties of Nanodiamond......Page 378
5.4.3 Mechanical Properties of Nanodiamond......Page 381
5.5.1 Reactivity of Nanodiamond......Page 383
5.5.2.1 Hydrogenation......Page 386
5.5.2.2 Halogenation......Page 387
5.5.2.3 Oxidation of Nanodiamond......Page 389
5.5.2.5 Silanization of Nanodiamond......Page 390
5.5.2.6 Alkylation and Arylation of Nanodiamond......Page 391
5.5.2.7 Reactions on sp2-Hybridized Domains on the Nanodiamond Surface......Page 392
5.5.2.8 Further Functionalization of Nanodiamond......Page 393
5.5.2.9 Composites and Noncovalent Interactions with Nanodiamond......Page 396
5.6.1 Mechanical Applications......Page 398
5.6.3 Applications as Sorbent......Page 400
5.6.5 Further Applications and Perspectives......Page 401
5.7 Summary......Page 402
6.1 Discovery and History of Diamond Films......Page 405
6.2.1 General Considerations on the Structure of Diamond Films......Page 407
6.2.2.1 Structure of the (111)-Plane......Page 410
6.2.2.2 Structure of the (100)-Plane......Page 412
6.2.2.3 Structure of the (110)-Plane......Page 414
6.2.3 Defects and Doping of Diamond Films......Page 415
6.2.4 Structure of Further Diamond-Like Film Materials......Page 418
6.3.1 CVD Methods for the Preparation of Diamond Films......Page 419
6.3.1.1 Hot Filament CVD......Page 420
6.3.1.3 Microwave CVD......Page 421
6.3.2 Growth Mechanism of Diamond Films......Page 423
6.3.3 Preparation of UNCD......Page 426
6.3.4 Further Methods of Diamond Film Production......Page 428
6.4.1.1 Infrared and Raman Spectroscopy......Page 429
6.4.1.2 Optical Properties of Diamond Films......Page 432
6.4.1.3 XRD, XPS, and EELS of Diamond Films......Page 434
6.4.2 Electronic Properties of Diamond Films......Page 436
6.4.2.1 Electric Conductivity of Diamond Films......Page 437
6.4.2.2 Field Emission from Diamond Films......Page 439
6.4.3 Mechanical Properties of Diamond Films......Page 440
6.5.1 Considerations on the Reactivity of Diamond Films......Page 444
6.5.2.2 Halogenation of Diamond Films......Page 446
6.5.2.3 Oxidation of Diamond Surfaces......Page 448
6.5.2.4 Radical and Photochemical Reactions on Diamond Surfaces......Page 449
6.5.2.5 Cycloadditions on Diamond Surfaces......Page 452
6.5.2.6 Further Reactions on Functionalized Diamond Films......Page 454
6.5.4 Electrochemistry of Diamond Films......Page 456
6.6.1 Mechanical Applications......Page 459
6.6.2 Electronic Applications......Page 460
6.6.3 Chemical, Electrochemical, and Biological Applications......Page 462
6.6.4 Further Applications of Diamond Films......Page 463
6.7 Summary......Page 464
7: Epilog......Page 467
Fullerenes......Page 471
Carbon Nanotubes......Page 472
Diamond Films......Page 473
8.2 Figure References......Page 474
Index......Page 483
Paper Cutout DIY Kit......Page 491