Preface ......................................................... v
Contributing authors ......................................... xvii
Part I: Nanocarbon building blocks
Paul Gebhardt and Dominik Eder
1 A short introduction on carbon nanotubes ................... 3
1.1 Introduction ............................................... 3
1.2 Structural aspects ......................................... 4
1.2.1 Chirality ........................................... 4
1.2.2 Defects ............................................. 5
1.2.3 Doping .............................................. 6
1.3 Properties of CNTs ......................................... 7
1.3.1 Mechanical properties ............................... 7
1.3.2 Electronic properties ............................... 8
1.3.3 Thermal properties .................................. 9
1.4 Characterization .......................................... 10
1.5 Synthesis ................................................. 11
1.5.1 Laser ablation ..................................... 12
1.5.2 Arc discharge ...................................... 12
1.5.3 Molten salt route / electrolytic process ........... 13
1.5.4 Chemical vapor deposition (CVD) .................... 13
1.6 Post-synthesis treatments ................................. 14
1.6.1 Purification ....................................... 14
1.6.2 Separation of metallic and semiconducting CNTs
1.6.3 Functionalization .................................. 16
1.6.4 Assembly ........................................... 18
1.7 Summary ................................................... 18
Keith Paton
2 Synthesis, characterisation and properties of graphene .... 25
2.1 Introduction .............................................. 25
2.2 Properties ................................................ 25
2.3 Synthesis ................................................. 26
2.3.1 Micromechanical cleavage ........................... 26
2.3.2 Liquid phase exfoliation ........................... 27
2.3.3 Precipitation from metals/CVD ...................... 30
2.3.4 Epitaxial growth from SiC .......................... 31
2.4 Characterization .......................................... 32
Michele Melchionna and Maurizio Prato
3 Functionalization of carbon nanotubes ..................... 43
3.1 Introduction .............................................. 43
3.2 Functionalization. Why? ................................... 44
3.3 Types of functionalization ................................ 46
3.3.1 Covalent functionalization ......................... 46
3.3.2 Noncovalent functionalization ...................... 54
3.4 Functionalization with metals ............................. 61
3.5 Summary ................................................... 65
S.M. Vega-Diaz, F. Tristán López, A. Morelos-Gómez,
R. Cruz-Silva, and M. Terrones
4 The importance of defects and dopants within carbon
nanomaterials during the fabrication of polymer
composites ................................................ 71
4.1 Introduction .............................................. 71
4.1.1 Carbon nanostructures and their properties ......... 72
4.1.2 Doped carbon nanostructures ........................ 74
4.1.3 Defects in carbon nanostructures ................... 76
4.1.4 Functionalization of carbon nanostructures for
nanocomposites ..................................... 79
4.2 Incorporation of nanocarbons into polymer composites
and hybrids ............................................... 83
4.2.1 Types of polymer composites ........................ 83
4.2.2 Synthesis approaches ............................... 86
4.3 Properties ................................................ 89
4.3.1 Mechanical properties .............................. 89
4.3.2 Thermal properties ................................. 93
4.3.3 Electrical properties .............................. 95
4.3.4 Optical properties ................................. 97
4.3.5 Biocompatibility ................................... 98
4.3.6 Biodegradation ..................................... 99
4.3.7 Permeability ...................................... 102
4.4 Summary .................................................. 104
Part II: Synthesis and characterisation of hybrids
Cameron J. Shearer and Dominik Eder
5 Synthesis strategies of nanocarbon hybrids ............... 125
5.1 Introduction ............................................. 125
5.2 Exsitu approaches ........................................ 127
5.2.1 Covalent interactions ............................. 127
5.2.2 Noncovalent interactions .......................... 129
5.3 In situ approaches ....................................... 134
5.3.1 In situ polymerization ............................ 135
5.3.2 Inorganic hybridization from metal salts .......... 137
5.3.3 Electrochemical processes ......................... 142
5.3.4 Sol-gel processes ................................. 146
5.3.5 Gas phase deposition .............................. 148
5.4 Other nanocarbons ........................................ 152
5.5 Comparison of synthesis techniques ....................... 153
5.6 Summary .................................................. 154
C.N.R. Rao, H.S.S. Ramakrishna Matte, and Urmimala Maitra
6 Graphene and its hybrids with inorganic nanoparticles,
polymers and other materials ............................. 171
6.1 Introduction ............................................. 171
6.2 Synthesis ................................................ 172
6.3 Nanocarbon (graphene/C60/SWNT) hybrids ................... 175
6.4 Graphene-polymer composites .............................. 178
6.5 Functionalization of graphene and related aspects ........ 182
6.6 Graphene-inorganic nanoparticle hybrids .................. 185
6.7 Graphene hybrids with Sn02, MoS2 and WS2 as anodes in
batteries ................................................ 189
6.8 Graphene-MOF hybrids ..................................... 192
6.9 Summary .................................................. 195
Markus Antonietti, Li Zhao, and Maria-Magdalena Titirici
7 Sustainable carbon hybrid materials made by
hydrothermal carbonization and their use in energy
applications ............................................. 201
7.1 Introduction ............................................. 201
7.2 Hydrothermal synthesis of carbonaceous materials ......... 202
7.2.1 From pure carbohydrates ........................... 202
7.2.2 From complex biomass .............................. 209
7.2.3 Energy applications of hydrothermal carbons and
their hybrids ..................................... 210
7.3 Summary .................................................. 221
Juan J. Vilatela
8 Nanocarbon-based composites .............................. 227
8.1 Introduction ............................................. 227
8.2 Integration routes: From filler to other more complex
structures ............................................... 228
8.2.1 Filler route ...................................... 229
8.2.2 Evaluation of reinforcement ....................... 230
8.2.3 Other properties .................................. 232
8.3 Hierarchical route ....................................... 235
8.3.1 Structure and improvement in properties ........... 236
8.3.2 Other properties .................................. 238
8.4 Fiber route .............................................. 240
8.4.1 Different assembly routes ......................... 241
8.4.2 Assembly properties and structure ................. 243
8.4.3 Assembly composites ............................... 245
8.4.4 Other properties of nanocarbon assemblies ......... 248
8.5 Summary .................................................. 248
Robert Schlögl
9 Carbon-Carbon Composites ................................. 255
9.1 Introduction ............................................. 255
9.2 Typology of C3 materials ................................. 256
9.3 Synthesis ................................................ 259
9.4 Identification of the structural features of C3
material ................................................. 264
9.5 Surface chemistry ........................................ 266
9.6 Summary .................................................. 268
Teresa J. Bandosz
10 Graphite oxide-MOF hybrid materials ...................... 273
10.1 Introduction ............................................. 273
10.2 Building blocks .......................................... 274
10.2.1 Graphite oxide .................................... 274
10.2.2 Metal Organic Frameworks: MOF-5, HKUST-1 and
MIL-lOO(Fe) ....................................... 275
10.3 Building the hybrid materials: Surface texture and
chemistry ................................................ 276
10.4 MOF-Graphite oxides composites as adsorbents of toxic
gases .................................................... 281
10.4.1 Ammonia ........................................... 282
10.4.2 Nitrogen dioxide .................................. 284
10.4.3 Hydrogen sulfide .................................. 286
10.5 Beyond the MOF-Graphite oxides composites ................ 288
10.6 Summary .................................................. 289
Part III: Applications of nanocarbon hybrids
Dang Sheng Su
11 Batteries/Supercapacitors: Hybrids with CNTs ............. 297
11.1 Introduction ............................................. 297
11.2 Application of hybrids with CNTs for batteries ........... 298
11.2.1 Lithium ion battery ............................... 298
11.2.2 Lithium sulfur battery ............................ 307
11.2.3 Lithium air battery ............................... 308
11.3 Application of hybrids with CNTs in supercapacitor ....... 310
11.3.1 CNT-based carbon hybrid for supercapacitors ....... 311
11.3.2 CNT-based inorganic hybrid for supercapacitors .... 313
11.4 Summary .................................................. 314
Zhong-Shuai Wu, Xinliang Feng, and Klaus Müllen
12 Graphene-metal oxide hybrids for lithium ion batteries
and electrochemical capacitors ........................... 319
12.1 Introduction ............................................. 319
12.2 Graphene for LIBs and ECs ................................ 320
12.3 Graphene-metal oxide hybrids in LIBs and ECs ............. 321
12.3.1 Typical structural models of graphene-metal
oxide hybrids ..................................... 321
12.3.2 Anchored model .................................... 323
12.3.3 Encapsulated model ................................ 327
12.3.4 Sandwich-like model ............................... 330
12.3.5 Layered model ..................................... 332
12.3.6 Mixed models ...................................... 335
12.4 Summary .................................................. 336
John Robertson
13 Nanocarbons for field emission devices ................... 341
13.1 Introduction ............................................. 341
13.2 Carbon nanotubes- general considerations ................. 343
13.2.1 Field emission from nanocarbons ................... 346
13.2.2 Emission from nanowallsand CNTs walls ............. 346
13.3 Applications ............................................. 347
13.3.1 Field emission electron guns for electron
microscopes ....................................... 347
13.3.2 Displays .......................................... 348
13.3.3 Microtriodes and E-beam lithography ............... 349
13.3.4 Microwave power amplifiers ........................ 351
13.3.5 Ionization gauges ................................. 352
13.3.6 Pulsed X-ray sources and tomography ............... 352
13.4 Summary .................................................. 353
Panagiotis Trogadas and Peter Strasser
14 Carbon, carbon hybrids and composites for polymer
electrolyte fuel cells ................................... 357
14.1 Introduction ............................................. 357
14.2 Carbon as electrode and electrocatalyst .................. 357
14.2.1 Structure and properties .......................... 357
14.2.2 Electrochemical properties ........................ 360
14.2.3 Applications ...................................... 362
14.3 Carbon, carbon hybrids and carbon composites in PEFCs .... 368
14.3.1 Carbon as structural component in PEFCs ........... 368
14.3.2 Carbon as PEFC catalyst support ................... 369
14.3.3 Carbon hybrids and composites as ORR
electrocatalysts .................................. 379
14.4 Summary .................................................. 385
Benjamin Frank
15 Nanocarbon materials for heterogeneous catalysis ......... 393
15.1 Introduction ............................................. 393
15.2 Relevant properties of nanocarbons ....................... 394
15.2.1 Textural properties and macroscopic shaping ....... 394
15.2.2 Surface chemistry and functionalization ........... 397
15.2.3 Confinement effect ................................ 400
15.3 Nanocarbon-based catalysts ............................... 401
15.3.1 Dehydrogenation of Hydrocarbons ................... 402
15.3.2 Dehydrogenations of alcohols ...................... 407
15.3.3 Other reactions ................................... 410
15.4 Nanocarbon as catalyst support ...................... 412
15.4.1 Catalyst preparation strategies ................... 412
15.4.2 Applications in heterogeneous catalysis ........... 416
15.5 Summary .................................................. 422
Gabriele Centi and Siglinda Perathoner
16 Advanced photocatalytic materials by nanocarbon hybrid
materials ................................................ 429
16.1 Introduction ............................................. 429
16.1.1 Hybrid vs. composite nanomaterials ................ 430
16.1.2 Use of nanocarbon hybrid materialsin
photoreactions .................................... 432
16.2 Nanocarbon characteristics ............................... 433
16.2.1 The role of defects ............................... 435
16.2.2 Modification of nanocarbons ....................... 437
16.2.3 New aspects ....................................... 437
16.2.4 Nanocarbon quantum dots ........................... 438
16.3 Mechanisms of nanocarbon promotion in photoactivated
processes ................................................ 440
16.4 Advantages of nanocarbon-semiconductor hybrid
materials ........................................... 443
16.5 Nanocarbon-semiconductor hybrid materials for
sustainable energy .................................. 447
16.6 Summary .................................................. 448
Jiangtao Di, Zhigang Zhao, and Qingwen Li
17 Electrochromic and photovoltaic applications of
nanocarbon hybrids ....................................... 455
17.1 Introduction ............................................. 455
17.2 Nanocarbon Hybrids for electrochromic materials and
devices .................................................. 456
17.2.1 Intrinsic electrochromism of nanocarbons .......... 456
17.2.2 Synthesis and electrochromic properties of
nanocarbon-metal oxide hybrids .................... 457
17.2.3 Electrochromic properties of nanocarbon-polymer
hybrids ........................................... 459
17.3 Nanocarbon hybrids for photovoltaic applications ......... 461
17.3.1 Working mechanisms of PECs and OPVs ............... 461
17.3.2 Nanocarbon hybrids for PECs ....................... 462
17.3.3 Nanocarbon hybrids for OPVs ....................... 468
17.4 Summary .................................................. 469
Rubén D. Costa and Dirk M. Guldi
18 Carbon nanomaterials as integrative components in
dye-sensitized solar cells ............................... 475
18.1 Today's dye-sensitized solar cells. Definition and
potential ................................................ 475
18.2 Major challenges in improving the performance of DSSCs ... 477
18.3 Carbon nanomaterials as integrative materials in
semiconducting electrodes ................................ 479
18.3.1 Interlayers made out of carbon nanomaterials ...... 479
18.3.2 Implementation of carbon nanomaterials into
electrode networks ................................ 480
18.4 Carbon nanomaterials for solid-state electrolytes ........ 484
18.4.1 Fullerene-based solid-state electrolytes .......... 484
18.4.2 CNTs-based solid-state electrolytes ............... 485
18.4.3 Graphene-based solid-state electrolytes ........... 487
18.5 Versatility of carbon nanomaterials-based hybrids as
novel type of dyes ....................................... 488
18.5.1 Fullerene-based dyes .............................. 488
18.5.2 Graphene-based dyes ............................... 490
18.6 Photoelectrodes prepared by nanographene hybrids ......... 492
18.6.1 Preparation of photoelectrodes by using
noncovalently functionalized graphene ............. 492
18.6.2 Preparation of photoelectrodes by preparing
nanographene-based building blocks via
electrostatic interactions ........................ 494
18.7 Summary .................................................. 496
Ljubisa R. Radovic
19 Importance of edge atoms ................................. 503
19.1 Introduction ............................................. 503
19.2 External edges ........................................... 505
19.3 Internal edges ........................................... 515
19.4 Edge reconstruction ...................................... 519
19.5 Summary .................................................. 522
Index ......................................................... 527
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