Carbon Materials and Nanotechnology

Carbon Materials and Nanotechnology......Page 6
Contents......Page 8
Preface......Page 16
1.1 History......Page 18
1.2 Structure and Bonding......Page 23
1.2.1 Graphite and Its Structure......Page 24
1.2.2 Diamond and Its Structure......Page 26
1.2.3 Structure of Other Carbon Allotropes......Page 27
1.3.1 Graphite and Related Materials......Page 30
1.3.2 Diamond......Page 34
1.4 Physical Properties......Page 37
1.4.1 Graphite and Related Materials......Page 38
1.4.2 Diamond......Page 40
1.5 Chemical Properties......Page 41
1.5.1 Graphite and Related Materials......Page 43
1.6 Application and Perspectives......Page 46
1.6.3 Other Carbon Materials......Page 47
1.7 Summary......Page 48
2.1.1 Theoretical Predictions......Page 50
2.1.2 Experimental Proof......Page 51
2.2.1 Nomenclature......Page 53
2.2.2 The Structure of C60......Page 54
2.2.3 Structure of Higher Fullerenes and Growth Mechanisms......Page 57
2.2.4 Structure of Smaller Carbon Clusters......Page 62
2.2.5 Structure of Heterofullerenes......Page 63
2.3 Occurrence, Production, and Purification......Page 64
2.3.1 Fullerene Preparation by Pyrolysis of Hydrocarbons......Page 65
2.3.2 Partial Combustion of Hydrocarbons......Page 66
2.3.3 Arc Discharge Methods......Page 67
2.3.4 Production by Resistive Heating......Page 68
2.3.5 Rational Syntheses......Page 69
2.3.6 Enrichment and Purification......Page 71
2.3.7 Preparation of Heterofullerenes......Page 73
2.4.1.1 Solubility......Page 74
2.4.1.2 Spectroscopic Properties......Page 76
2.4.1.3 Thermodynamic Properties......Page 80
2.4.1.4 Solid C60......Page 81
2.4.2 Properties of Higher Fullerenes......Page 82
2.5 Chemical Properties......Page 83
2.5.1.1 Typical Reactions of Fullerenes......Page 84
2.5.1.3 Secondary and Multiple Additions......Page 85
2.5.2.1 Electrochemistry of Fullerenes......Page 89
2.5.2.2 Reductions of Fullerenes......Page 91
2.5.2.3 Oxidations of Fullerenes......Page 93
2.5.3 Inorganic Chemistry of Fullerenes......Page 94
2.5.4.1 Metallofullerenes......Page 99
2.5.4.2 Endohedral Compounds with Nonmetallic Elements......Page 103
2.5.5.1 Hydrogenation and Halogenation......Page 104
2.5.5.2 Nucleophilic Addition to Fullerenes......Page 110
2.5.5.3 Cycloadditions......Page 115
2.5.5.4 Photochemistry......Page 120
2.5.5.5 Radical Chemistry of Fullerenes......Page 122
2.5.5.6 Fullerenes in Polymeric Materials and on Surfaces......Page 124
2.5.6 Supramolecular Chemistry of Fullerenes......Page 129
2.5.7 Polymeric Fullerenes and Behavior under High Pressure......Page 133
2.5.8 Reactivity of Further Fullerenes......Page 134
2.6 Applications and Perspectives......Page 135
2.7 Summary......Page 138
3.1 Introduction......Page 140
3.2.1 Nomenclature......Page 143
3.2.2 Structure of Single-Walled Carbon Nanotubes......Page 144
3.2.3 Structure of Multiwalled Carbon Nanotubes......Page 152
3.3.1.1 Arc Discharge Methods......Page 157
3.3.1.2 Laser Ablation......Page 159
3.3.1.3 The HiPCo Process......Page 161
3.3.1.4 Pyrolysis......Page 163
3.3.1.5 Chemical Vapor Deposition (CVD)......Page 164
3.3.2.1 Arc Discharge Methods......Page 167
3.3.2.2 Laser Ablation......Page 170
3.3.2.3 Chemical Vapor Deposition (CVD)......Page 171
3.3.2.4 Decomposition of Hydrocarbons– Pyrolytic Methods......Page 173
3.3.2.5 Production of Double-Walled Carbon Nanotubes......Page 175
3.3.3 Strategies for the Rational Synthesis of Carbon Nanotubes......Page 176
3.3.4.1 Bamboo-Like Carbon Nanotubes......Page 180
3.3.4.2 Cup-Stacked Carbon Nanotubes......Page 181
3.3.4.3 Carbon Nanohorns (SWNH)......Page 182
3.3.4.4 Helical Carbon Nanotubes (hMWNT)......Page 183
3.3.5 Arrays of Carbon Nanotubes......Page 185
3.3.6.1 Removal of Impurities from Carbon Nanotube Materials......Page 188
3.3.6.2 Evaluating the Purity of Carbon Nanotube Materials......Page 190
3.3.6.3 Cutting of Carbon Nanotubes......Page 193
3.3.6.4 Separation of Carbon Nanotubes by their Properties......Page 194
3.3.7.1 Arc Discharge Methods......Page 197
3.3.7.2 CVD-Methods......Page 202
3.4.1 General Considerations......Page 203
3.4.2 Solubility and Debundling of Carbon Nanotubes......Page 204
3.4.3 Mechanical Properties of Carbon Nanotubes......Page 207
3.4.4.1 Band Structure and Density of States of Carbon Nanotubes......Page 211
3.4.4.2 The Mechanism of Electric Conduction in Carbon Nanotubes......Page 219
3.4.4.3 Field Emission from Carbon Nanotubes......Page 221
3.4.5.1 Raman and Infrared Spectroscopy of Carbon Nanotubes......Page 223
3.4.5.2 Absorption and Emission Spectroscopy of Carbon Nanotubes......Page 226
3.4.5.3 ESR-Spectroscopic Properties of Carbon Nanotubes......Page 229
3.4.5.4 Further Spectroscopic Properties of Carbon Nanotubes......Page 230
3.4.6.2 Heat Conductivity of Carbon Nanotubes......Page 233
3.5.1 General Considerations on the Reactivity of Carbon Nanotubes......Page 234
3.5.2 Redox Chemistry of Carbon Nanotubes......Page 237
3.5.3 Functionalization of the Caps or Open Ends of Carbon Nanotubes......Page 241
3.5.4.1 Covalent Attachment of the Functional Groups......Page 243
3.5.4.2 Noncovalent Attachment of Functional Units......Page 257
3.5.5 Composite Materials with Carbon Nanotubes......Page 263
3.5.5.1 Composites with Covalent Bonding of the Polymer......Page 265
3.5.5.2 Composites with Noncovalent Attachment of the Polymer......Page 266
3.5.5.3 Nanotube Composites with Different Polymers......Page 267
3.5.5.4 Nanotube Composites with Other Materials......Page 271
3.5.6 Intercalation Compounds and Endohedral Functionalization of Carbon Nanotubes......Page 272
3.5.7 Supramolecular Chemistry of Carbon Nanotubes......Page 280
3.6 Applications and Perspectives......Page 283
3.6.1.1 Nanotubes as Tips in Atomic Force Microscopy......Page 284
3.6.1.2 Field Emission......Page 285
3.6.1.3 Field Effect Transistors......Page 286
3.6.2.2 Chemical Sensors......Page 288
3.6.3.1 Recognition of DNA Sequences......Page 290
3.6.3.2 Delivery of Drugs and Vaccines; Gene Therapy......Page 291
3.6.4 Materials with Carbon Nanotubes......Page 292
3.6.5.1 Heterogeneous Catalysis......Page 294
3.6.5.2 Hydrogen Storage in Carbon Nanotubes......Page 295
3.6.5.3 Carbon Nanotubes as Material in Electrical Engineering......Page 296
3.7 Summary......Page 297
4.1 Introduction......Page 300
4.2.1 Structure of Carbon Onions......Page 301
4.2.2 Structure of Faceted Carbon Nanoparticles......Page 306
4.2.3 Occurrence of Carbon Onions and Nanoparticles......Page 307
4.3.1 Arc Discharge Methods......Page 308
4.3.2 CVD-Methods......Page 310
4.3.3 Preparation of Carbon Onions by Ion Bombardment......Page 311
4.3.4 Chemical Methods......Page 313
4.3.5.1 Thermal Transformations of Soot-Like Structures......Page 315
4.3.5.2 Irradiation of Soot-Like and Other sp2-Hybridized Carbons......Page 317
4.3.5.3 Thermal Transformation of Diamond......Page 320
4.3.5.4 Irradiation of Diamond Materials......Page 321
4.3.6 Further Methods to Produce Carbon Onions......Page 322
4.3.7.1 Growth Mechanisms of Carbon Onions Obtained by Electron Irradiation......Page 324
4.3.7.2 Growth Mechanisms of Carbon Onions Obtained by Thermal Treatment......Page 326
4.4.1 Spectroscopic Properties......Page 330
4.4.1.1 IR- and Raman Spectroscopy......Page 331
4.4.1.2 X-Ray Diffraction......Page 332
4.4.1.3 Absorption Spectra of Carbon Onions and Related Materials......Page 333
4.4.1.4 EEL-Spectra of Carbon Onions and Related Materials......Page 334
4.4.1.5 Further Spectroscopic Properties of Carbon Onions and Related Materials......Page 335
4.4.2 Thermodynamic Properties......Page 336
4.4.3 Electronic Properties......Page 337
4.5.1 Reactivity and Functionalization of Carbon Onions and Carbon Nanoparticles......Page 338
4.5.2 Conversion into Other Forms of Carbon......Page 340
4.6 Applications and Perspectives......Page 341
4.6.1 Tribological Applications......Page 342
4.6.2 Applications in Catalysis......Page 343
4.7 Summary......Page 344
5.1.1 Historical Background to the Discovery of Nanodiamonds......Page 346
5.1.2 Natural Occurrence of Nanodiamond......Page 348
5.2.1 The Lattice Structure of Nanodiamond......Page 349
5.2.2 The Surface Structure of Nanodiamond......Page 350
5.2.3 Diamond or Graphite? Stability in the Nanometer Range......Page 353
5.2.4 Agglomeration of Nanodiamond......Page 355
5.3.1 Detonation Synthesis......Page 357
5.3.2 Shock Syntheses of Nanodiamond......Page 361
5.3.3 Further Methods of Nanodiamond Preparation......Page 363
5.3.4 Deagglomeration and Purification......Page 366
5.4.1.1 Raman Spectroscopy......Page 368
5.4.1.2 Infrared Spectroscopy......Page 371
5.4.1.3 X-Ray Diffraction and EELS......Page 373
5.4.1.4 Absorption and Photoluminescence Spectroscopy......Page 375
5.4.1.5 Further Spectroscopic Properties......Page 377
5.4.2 Electronic Properties of Nanodiamond......Page 379
5.4.3 Mechanical Properties of Nanodiamond......Page 382
5.5.1 Reactivity of Nanodiamond......Page 384
5.5.2.1 Hydrogenation......Page 387
5.5.2.2 Halogenation......Page 388
5.5.2.3 Oxidation of Nanodiamond......Page 390
5.5.2.5 Silanization of Nanodiamond......Page 391
5.5.2.6 Alkylation and Arylation of Nanodiamond......Page 392
5.5.2.7 Reactions on sp2-Hybridized Domains on the Nanodiamond Surface......Page 393
5.5.2.8 Further Functionalization of Nanodiamond......Page 394
5.5.2.9 Composites and Noncovalent Interactions with Nanodiamond......Page 397
5.6.1 Mechanical Applications......Page 399
5.6.3 Applications as Sorbent......Page 401
5.6.5 Further Applications and Perspectives......Page 402
5.7 Summary......Page 403
6.1 Discovery and History of Diamond Films......Page 406
6.2.1 General Considerations on the Structure of Diamond Films......Page 408
6.2.2.1 Structure of the (111)-Plane......Page 411
6.2.2.2 Structure of the (100)-Plane......Page 413
6.2.2.3 Structure of the (110)-Plane......Page 415
6.2.3 Defects and Doping of Diamond Films......Page 416
6.2.4 Structure of Further Diamond-Like Film Materials......Page 419
6.3.1 CVD Methods for the Preparation of Diamond Films......Page 420
6.3.1.1 Hot Filament CVD......Page 421
6.3.1.3 Microwave CVD......Page 422
6.3.2 Growth Mechanism of Diamond Films......Page 424
6.3.3 Preparation of UNCD......Page 427
6.3.4 Further Methods of Diamond Film Production......Page 429
6.4.1.1 Infrared and Raman Spectroscopy......Page 430
6.4.1.2 Optical Properties of Diamond Films......Page 433
6.4.1.3 XRD, XPS, and EELS of Diamond Films......Page 435
6.4.2 Electronic Properties of Diamond Films......Page 437
6.4.2.1 Electric Conductivity of Diamond Films......Page 438
6.4.2.2 Field Emission from Diamond Films......Page 440
6.4.3 Mechanical Properties of Diamond Films......Page 441
6.5.1 Considerations on the Reactivity of Diamond Films......Page 445
6.5.2.2 Halogenation of Diamond Films......Page 447
6.5.2.3 Oxidation of Diamond Surfaces......Page 449
6.5.2.4 Radical and Photochemical Reactions on Diamond Surfaces......Page 450
6.5.2.5 Cycloadditions on Diamond Surfaces......Page 453
6.5.2.6 Further Reactions on Functionalized Diamond Films......Page 455
6.5.4 Electrochemistry of Diamond Films......Page 457
6.6.1 Mechanical Applications......Page 460
6.6.2 Electronic Applications......Page 461
6.6.3 Chemical, Electrochemical, and Biological Applications......Page 463
6.6.4 Further Applications of Diamond Films......Page 464
6.7 Summary......Page 465
7: Epilog......Page 468
Fullerenes......Page 472
Carbon Nanotubes......Page 473
Diamond Films......Page 474
8.2 Figure References......Page 475
Index......Page 484
Paper Cutout DIY Kit......Page 492