Preface ...................................................... XIII
1 Carbon-Element of Many Faces ................................. 7
1.1 History ................................................. 1
1.2 Structure and Bonding ................................... 6
1.2.1 Graphite and Its Structure ....................... 7
1.2.2 Diamond and Its Structure ........................ 9
1.2.3 Structure of Other Carbon Allotropes ............ 10
1.2.4 Liquid and Gaseous Carbon ....................... 13
1.3 Occurrence and Production .............................. 13
1.3.1 Graphite and Related Materials .................. 13
1.3.2 Diamond ......................................... 17
1.4 Physical Properties .................................... 20
1.4.1 Graphite and Related Materials .................. 21
1.4.2 Diamond ......................................... 23
1.5 Chemical Properties .................................... 24
1.5.1 Graphite and Related Materials .................. 26
1.5.2 Diamond ......................................... 29
1.6 Application and Perspectives ........................... 29
1.6.1 Graphite and Related Materials .................. 30
1.6.2 Diamond ......................................... 30
1.6.3 Other Carbon Materials .......................... 30
1.7 Summary ................................................ 31
2 Fullerenes-Cages Made from Carbon ........................... 33
2.1 History-The Discovery of New Carbon Allotropes ......... 33
2.1.1 Theoretical Predictions ......................... 33
2.1.2 Experimental Proof .............................. 34
2.2 Structure and Bonding .................................. 36
2.2.1 Nomenclature .................................... 36
2.2.2 The Structure of C60 ............................ 37
2.2.3 Structure of Higher Fullerenes and Growth
Mechanisms ...................................... 40
2.2.4 Structure of Smaller Carbon Clusters ............ 45
2.2.5 Structure of Heterofullerenes ................... 46
2.3 Occurrence, Production, and Purification ............... 47
2.3.1 Fullerene Preparation by Pyrolysis of
Hydrocarbons .................................... 48
2.3.2 Partial Combustion of Hydrocarbons .............. 49
2.3.3 Arc Discharge Methods ........................... 50
2.3.4 Production by Resistive Heating ................. 51
2.3.5 Rational Syntheses .............................. 52
2.3.6 Enrichment and Purification ..................... 54
2.3.7 Preparation of Heterofullerenes ................. 56
2.4 Physical Properties .................................... 57
2.4.1 Properties of C60 and C70 ........................ 57
2.4.1.1 Solubility ............................. 57
2.4.1.2 Spectroscopic Properties ............... 59
2.4.1.3 Thermodynamic Properties ............... 63
2.4.1.4 Solid C60 .............................. 64
2.4.2 Properties of Higher Fullerenes ................. 65
2.5 Chemical Properties .................................... 66
2.5.1 General Considerations on Fullerene Chemistry ... 67
2.5.1.1 Typical Reactions of Fullerenes ........ 67
2.5.1.2 Regiochemistry of Additions to
Fullerenes ............................. 68
2.5.1.3 Secondary and Multiple Additions ....... 68
2.5.2 Electro-and Redox Chemistry of Fullerenes ....... 72
2.5.2.1 Electrochemistry of Fullerenes ......... 72
2.5.2.2 Reductions of Fullerenes ............... 74
2.5.2.3 Oxidations of Fullerenes ............... 76
2.5.3 Inorganic Chemistry of Fullerenes ............... 77
2.5.4 Endohedral Complexes of Fullerenes .............. 82
2.5.4.1 Metallofullerenes ...................... 82
2.5.4.2 Endohedral Compounds with Nonmetallic
Elements ............................... 86
2.5.5 Organic Chemistry of Fullerenes ................. 87
2.5.5.1 Hydrogenation and Halogenation ......... 87
2.5.5.2 Nucleophilic Addition to Fullerenes .... 93
2.5.5.3 Cycloadditions ......................... 98
2.5.5.4 Photochemistry ........................ 103
2.5.5.5 Radical Chemistry of Fullerenes ....... 105
2.5.5.6 Fullerenes in Polymeric Materials
and on Surfaces ....................... 107
2.5.6 Supramolecular Chemistry of Fullerenes ......... 112
2.5.7 Polymeric Fullerenes and Behavior under High
Pressure ....................................... 116
2.5.8 Reactivity of Further Fullerenes ............... 117
2.6 Applications and Perspectives ......................... 118
2.7 Summary ............................................... 121
3 Carbon Nanotubes ........................................... 723
3.2 The Structure of Carbon Nanotubes ..................... 126
3.2.1 Nomenclature ................................... 126
3.2.2 Structure of Single-Walled Carbon Nanotubes .... 127
3.2.3 Structure of Multiwalled Carbon Nanotubes ...... 135
3.3 Production and Purification of Carbon Nanotubes ....... 140
3.3.1 Production of Single-Walled Carbon Nanotubes ... 140
3.3.1.1 Arc Discharge Methods ................. 140
3.3.1.2 Laser Ablation ........................ 142
3.3.1.3 The HiPCo Process ..................... 144
3.3.1.4 Pyrolysis ............................. 146
3.3.1.5 Chemical Vapor Deposition (CVD) ....... 147
3.3.2 Production of Multiwalled Carbon Nanotubes ..... 150
3.3.2.1 Arc Discharge Methods ................. 150
3.3.2.2 Laser Ablation ........................ 153
3.3.2.3 Chemical Vapor Deposition (CVD) ....... 254
3.3.2.4 Decomposition of Hydrocarbons-
Pyrolytic Methods ..................... 156
3.3.2.5 Production of Double-Walled Carbon
Nanotubes ............................. 158
3.3.3 Strategies for the Rational Synthesis of
Carbon Nanotubes ............................... 159
3.3.4 Structure and Production of Further Tubular
Carbon Materials .............................. 163
3.3.4.1 Bamboo-Like Carbon Nanotubes .......... 163
3.3.4.2 Cup-Stacked Carbon Nanotubes .......... 164
3.3.4.3 Carbon Nanohorns (SWNH) ............... 165
3.3.4.4 Helical Carbon Nanotubes (hMWNT) ...... 166
3.3.5 Arrays of Carbon Nanotubes ..................... 168
3.3.6 Purification and Separation of Carbon
Nanotubes ...................................... 171
3.3.6.1 Removal of Impurities from Carbon
Nanotube Materials .................... 171
3.3.6.2 Evaluating the Purity of Carbon
Nanotube Materials .................... 173
3.3.6.3 Cutting of Carbon Nanotubes ........... 176
3.3.6.4 Separation of Carbon Nanotubes by
their Properties ...................... 177
3.3.7 The Growth Mechanism of Carbon Nanotubes ....... 180
3.3.7.1 Arc Discharge Methods ................. 180
3.3.7.2 CVD-Methods ........................... 185
3.4 Physical Properties ................................... 186
3.4.1 General Considerations ......................... 186
3.4.2 Solubility and Debundling of Carbon
Nanotubes ...................................... 187
3.4.3 Mechanical Properties of Carbon Nanotubes ...... 190
3.4.4 Electronic Properties of Carbon Nanotubes ...... 194
3.4.4.1 Band Structure and Density of States
of Carbon Nanotubes ................... 194
3.4.4.2 The Mechanism of Electric Conduction
in Carbon Nanotubes ................... 202
3.4.4.3 Field Emission from Carbon
Nanotubes ............................. 204
3.4.5 Spectroscopic Properties of Carbon Nanotubes ... 206
3.4.5.1 Raman and Infrared Spectroscopy of
Carbon Nanotubes ...................... 206
3.4.5.2 Absorption and Emission Spectroscopy
of Carbon Nanotubes ................... 209
3.4.5.3 ESR-Spectroscopic Properties of
Carbon Nanotubes ...................... 212
3.4.5.4 Further Spectroscopic Properties of
Carbon Nanotubes ...................... 213
3.4.6 Thermal Properties of Carbon Nanotubes ......... 216
3.4.6.1 Specific Heat Capacity of Carbon
Nanotubes ............................. 216
3.4.6.2 Heat Conductivity of Carbon
Nanotubes ............................. 216
3.5 Chemical Properties ................................... 217
3.5.1 General Considerations on the Reactivity of
Carbon Nanotubes ............................... 217
3.5.2 Redox Chemistry of Carbon Nanotubes ............ 220
3.5.3 Functionalization of the Caps or Open Ends of
Carbon Nanotubes ............................... 224
3.5.4 Side Wall Functionalization of Carbon
Nanotubes ...................................... 226
3.5.4.1 Covalent Attachment of the
Functional Groups ..................... 226
3.5.4.2 Noncovalent Attachment of Functional
Units ................................. 240
3.5.5 Composite Materials with Carbon Nanotubes ...... 246
3.5.5.1 Composites with Covalent Bonding of
the Polymer ........................... 248
3.5.5.2 Composites with Noncovalent
Attachment of the Polymer ............. 249
3.5.5.3 Nanotube Composites with Different
Polymers .............................. 250
3.5.5.4 Nanotube Composites with Other
Materials ............................. 254
3.5.6 Intercalation Compounds and Endohedral
Functionalization of Carbon Nanotubes .......... 255
3.5.7 Supramolecular Chemistry of Carbon Nanotubes ... 263
3.6 Applications and Perspectives ......................... 266
3.6.1 Electronic Applications of Carbon Nanotubes .... 267
3.6.1.1 Nanotubes as Tips in Atomic Force
Microscopy ............................ 267
3.6.1.2 Field Emission ........................ 268
3.6.1.3 Field Effect Transistors .............. 269
3.6.2 Sensor Applications of Carbon Nanotubes ........ 271
3.6.2.1 Physical Sensors ...................... 271
3.6.2.2 Chemical Sensors ...................... 271
3.6.3 Biological Applications of Carbon Nanotubes .... 273
3.6.3.1 Recognition of DNA Sequences .......... 273
3.6.3.2 Delivery of Drugs and Vaccines; Gene
Therapy ............................... 274
3.6.4 Materials with Carbon Nanotubes ................ 275
3.6.5 Further Applications of Carbon Nanotubes ....... 277
3.6.5.1 Heterogeneous Catalysis ............... 277
3.6.5.2 Hydrogen Storage in Carbon
Nanotubes ............................. 278
3.6.5.3 Carbon Nanotubes as Material in
Electrical Engineering ................ 279
3.7 Summary .......................................... 280
4 Carbon Onions and Related Materials ........................ 283
4.1 Introduction .......................................... 283
4.2 Structure and Occurrence .............................. 284
4.2.1 Structure of Carbon Onions ..................... 284
4.2.2 Structure of Faceted Carbon Nanoparticles ...... 289
4.2.3 Occurrence of Carbon Onions and
Nanoparticles .................................. 290
4.3 Preparation and Mechanisms of Formation ............... 291
4.3.1 Arc Discharge Methods .......................... 291
4.3.2 CVD-Methods .................................... 293
4.3.3 Preparation of Carbon Onions by Ion
Bombardment .................................... 294
4.3.4 Chemical Methods ............................... 296
4.3.5 Transformations of Other Carbon Species ........ 298
4.3.5.1 Thermal Transformations of Soot-Like
Structures ............................ 298
4.3.5.2 Irradiation of Soot-Like and Other
sp2-Hybridized Carbons ................ 300
4.3.5.3 Thermal Transformation of Diamond ..... 303
4.3.5.4 Irradiation of Diamond Materials ...... 304
4.3.6 Further Methods to Produce Carbon Onions ....... 305
4.3.7 Growth Mechanisms of Carbon Onions ............. 307
4.3.7.1 Growth Mechanisms of Carbon Onions
Obtained by Electron Irradiation ...... 307
4.3.7.2 Growth Mechanisms of Carbon Onions
Obtained by Thermal Treatment ......... 309
4.4 Physical Properties ................................... 313
4.4.1 Spectroscopic Properties ....................... 313
4.4.1.1 IR-and Raman Spectroscopy ............. 314
4.4.1.2 X-Ray Diffraction ..................... 315
4.4.1.3 Absorption Spectra of Carbon Onions
and Related Materials ................. 316
4.4.1.4 EEL-Spectra of Carbon Onions and
Related Materials ..................... 317
4.4.1.5 Further Spectroscopic Properties of
Carbon Onions and Related Materials ... 318
4.4.2 Thermodynamic Properties ....................... 319
4.4.3 Electronic Properties .......................... 320
4.5 Chemical Properties ................................... 321
4.5.1 Reactivity and Functionalization of Carbon
Onions and Carbon Nanoparticles ................ 321
4.5.2 Conversion into Other Forms of Carbon .......... 323
4.6 Applications and Perspectives ......................... 324
4.6.1 Tribological Applications ...................... 325
4.6.2 Applications in Catalysis ...................... 326
4.7 Summary ............................................... 327
5 Nanodiamond ................................................ 329
5.1 Introduction .......................................... 329
5.1.1 Historical Background to the Discovery of
Nanodiamonds ................................... 329
5.1.2 Natural Occurrence of Nanodiamond .............. 331
5.2 Structure of Nanodiamonds ............................. 332
5.2.1 The Lattice Structure of Nanodiamond ........... 332
5.2.2 The Surface Structure of Nanodiamond ........... 333
5.2.3 Diamond or Graphite? Stability in the
Nanometer Range ................................ 336
5.2.4 Agglomeration of Nanodiamond ................... 338
5.3 Preparation of Nanodiamond ............................ 340
5.3.1 Detonation Synthesis ........................... 340
5.3.2 Shock Syntheses of Nanodiamond ................. 344
5.3.3 Further Methods of Nanodiamond Preparation ..... 346
5.3.4 Deagglomeration and Purification ............... 349
5.4 Physical Properties ................................... 351
5.4.1 Spectroscopic Properties of Nanodiamond ........ 351
5.4.1.1 Raman Spectroscopy .................... 351
5.4.1.2 Infrared Spectroscopy ................. 354
5.4.1.3 X-Ray Diffraction and EELS ............ 356
5.4.1.4 Absorption and Photoluminescence
Spectroscopy .......................... 358
5.4.1.5 Further Spectroscopic Properties ...... 360
5.4.2 Electronic Properties of Nanodiamond ........... 362
5.4.3 Mechanical Properties of Nanodiamond ........... 365
5.5 Chemical Properties ................................... 367
5.5.1 Reactivity of Nanodiamond ...................... 367
5.5.2 Surface Functionalization of Nanodiamond ....... 370
5.5.2.1 Hydrogenation ......................... 370
5.5.2.2 Halogenation .......................... 371
5.5.2.3 Oxidation of Nanodiamond .............. 373
5.5.2.4 Reduction of Nanodiamond .............. 374
5.5.2.5 Silanization of Nanodiamond ........... 374
5.5.2.6 Alkylation and Arylation of
Nanodiamond ........................... 375
5.5.2.7 Reactions on sp2-Hybridized Domains
on the Nanodiamond Surface ............ 376
5.5.2.8 Further Functionalization of
Nanodiamond ........................... 377
5.5.2.9 Composites and Noncovalent
Interactions with Nanodiamond ......... 380
5.5.3 Transformations of Nanodiamond into Other
Forms of Carbon ................................ 382
5.6 Applications and Perspectives ......................... 382
5.6.1 Mechanical Applications ........................ 382
5.6.2 Thermal Applications ........................... 384
5.6.3 Applications as Sorbent ........................ 384
5.6.4 Biological Applications ........................ 385
5.6.5 Further Applications and Perspectives .......... 385
5.7 Summary ............................................... 386
6 Diamond Films .............................................. 389
6.1 Discovery and History of Diamond Films ................ 389
6.2 Structure of Diamond Films ............................ 391
6.2.1 General Considerations on the Structure of
Diamond Films .................................. 391
6.2.2 The Surface Structure of Diamond Films ......... 394
6.2.2.1 Structure of the (111)-Plane .......... 394
6.2.2.2 Structure of the (100)-Plane .......... 396
6.2.2.3 Structure of the (110)-Plane .......... 398
6.2.3 Defects and Doping of Diamond Films ............ 399
6.2.4 Structure of Further Diamond-Like Film
Materials ...................................... 402
6.3 Preparation of Diamond Films .......................... 403
6.3.1 CVD Methods for the Preparation of Diamond
Films .......................................... 403
6.3.1.1 Hot Filament CVD ...................... 404
6.3.1.2 CVD at Simultaneous Electric
Discharge ............................. 405
6.3.1.3 Microwave CVD ......................... 405
6.3.2 Growth Mechanism of Diamond Films .............. 407
6.3.3 Preparation of UNCD ............................ 410
6.4 Physical Properties of Diamond Films .................. 413
6.4.1 Spectroscopic Properties of Diamond Films ...... 413
6.4.1.1 Infrared and Raman Spectroscopy ....... 413
6.4.1.2 Optical Properties of Diamond Films ... 416
6.4.1.3 XRD, XPS, and EELS of Diamond Films ... 418
6.4.2 Electronic Properties of Diamond Films ......... 420
6.4.2.1 Electric Conductivity of Diamond
Films ................................. 421
6.4.2.2 Field Emission from Diamond Films ..... 423
6.4.3 Mechanical Properties of Diamond Films ......... 424
6.4.4 Thermal Properties of Diamond Films ............ 428
6.5 Chemical Properties of Diamond Films .................. 428
6.5.1 Considerations on the Reactivity of Diamond
Films .......................................... 428
6.5.2 Covalent Functionalization of Diamond Films .... 430
6.5.2.1 Hydrogenation of Diamond Films ........ 430
6.5.2.2 Halogenation of Diamond Films ......... 430
6.5.2.3 Oxidation of Diamond Surfaces ......... 432
6.5.2.4 Radical and Photochemical Reactions
on Diamond Surfaces ................... 433
6.5.2.5 Cycloadditions on Diamond Surfaces .... 436
6.5.2.6 Further Reactions on Functionalized
Diamond Films ......................... 438
6.5.3 Noncovalent Functionalization of Diamond
Films .......................................... 440
6.5.4 Electrochemistry of Diamond Films .............. 440
6.6 Applications and Perspectives ......................... 443
6.6.1 Mechanical Applications ........................ 443
6.6.2 Electronic Applications ........................ 444
6.6.3 Chemical, Electrochemical, and Biological
Applications ................................... 446
6.6.4 Further Applications of Diamond Films .......... 447
6.7 Summary ............................................... 448
7 Epilog ..................................................... 457
8 Further Readings and Figure References ..................... 455
8.1 Further Readings ...................................... 455
Carbon in General ..................................... 455
Fullerenes ............................................ 455
Carbon Nanotubes ...................................... 456
Carbon Onions ......................................... 457
Diamond Films ......................................... 457
Nanodiamond ........................................... 458
8.2 Figure References ..................................... 458
Index ......................................................... 467
Paper Cutout DIY Kit .......................................... 475
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