Contributors ................................................... XV
Preface ....................................................... XIX
1 Physicochemical Properties of Carbon Materials: A Brief
Overview ..................................................... 1
Ljubisa R. Radovic
1.1 Introduction ............................................ 1
1.2 Formation of Carbons .................................... 2
1.2.1 Gas Phase ........................................ 2
1.2.2 Liquid Phase ..................................... 3
1.2.3 Solid Phase ...................................... 4
1.3 Structure and Properties of Carbons ..................... 5
1.3.1 Macrostructure ................................... 5
1.3.2 Microstructure ................................... 8
1.3.3 Nanostracture .................................... 8
1.3.4 Bulk Properties ................................. 16
1.3.5 Surface Properties .............................. 19
1.4 Reactions of Carbons ................................... 23
1.4.1 Gas Phase ....................................... 23
1.4.2 Liquid Phase .................................... 25
1.4.3 Solid Phase .................................... 27
1.5 Conclusions ............................................ 33
References ............................................. 34
2 Surface Chemistry of Carbon Materials ....................... 45
Teresa J. Bandosz
2.1 Introduction ........................................... 45
2.2 Surface Functionalities ................................ 47
2.2.1 Oxygen-Containing Functionalities ............... 48
2.2.2 Nitrogen-Containing Functionalities ............. 50
2.2.3 Hydrogen-Carbon Species ......................... 51
2.2.4 Sulfur, Phosphorus, and Halogen
Functionalities ................................. 51
2.3 Surface Modifications .................................. 54
2.3.1 Oxidation ....................................... 54
2.3.2 Introduction of Nitrogen-Containing Species ..... 55
2.3.3 Introduction of Sulfur Functionality ............ 55
2.3.4 Halogenization .................................. 56
2.3.5 Impregnation and Dry Mixing ..................... 56
2.3.6 Heat Treatment .................................. 56
2.4 Characterization of Surface Chemistry .................. 58
2.4.1 Elemental Analysis .............................. 58
2.4.2 Titration ....................................... 58
2.4.3 pH of Carbons, Point of Zero Charge, and
Isoelectric Point ............................... 61
2.4.4 Spectroscopic Methods ........................... 63
2.4.5 Calorimetric Techniques ......................... 72
2.4.6 Inverse Gas Chromatography ...................... 75
2.4.7 Temperature-Programmed Desorption ............... 75
2.4.8 Characterization of Surface Functionalities by
Electrochemical Techniques ...................... 78
2.5 Role of Surface Chemistry in the Reactive Adsorption
on Activated Carbons ................................... 78
2.6 Role of Carbon Surface Chemistry in Catalysis .......... 80
References .................................................. 82
3 Molecular Simulations Applied to Adsorption on and
Reaction with Carbon ........................................ 93
Zhonghua (John) Zhu
3.1 Introduction ........................................... 93
3.2 Molecular Simulation Methods Applied to Carbon
Reactions .............................................. 94
3.2.1 Electronic Structure Methods (or Quantum
Mechanics Methods) .............................. 94
3.2.2 Molecular Dynamics Simulations .................. 97
3.2.3 Monte Carlo Simulations ......................... 98
3.3 Hydrogen Adsorption on and Reaction with Carbon ........ 98
3.3.1 Atomic Hydrogen Adsorption on the Basal Plane
of Graphite ..................................... 98
3.3.2 Reactivities of Graphite Edge Sites and
Hydrogen Reactions on These Sites .............. 101
3.3.3 Hydrogen Storage in Carbon Nanotubes ........... 104
3.4 Carbon Reactions with Oxygen-Containing Gases ......... 105
3.4.1 Carbon Reactions with Oxygen-Containing Gases
and the Unified Mechanism ...................... 106
3.4.2 Catalyzed Gas-Carbon Reactions ................. 110
3.4.3 More Specific Studies on NOx, H2, CO2, and
O2-Carbon Reactions ............................ 118
3.5 Metal-Carbon Interactions ............................. 122
3.6 Conclusions ........................................... 125
References ................................................. 126
4 Carbon as Catalyst Support ................................. 131
Francisco Rodríguez-Reinoso and Antonio Sepúlveda-
Escribano
4.1 Introduction .......................................... 131
4.2 Properties Affecting Carbon's Role as Catalyst
Support ............................................... 132
4.2.1 Surface Area and Porosity ...................... 132
4.2.2 Surface Chemical Properties .................... 134
4.2.3 Inertness ...................................... 136
4.3 Preparation of Carbon-Supported Catalysts ............. 137
4.3.1 Impregnation ................................... 137
4.3.2 Other Methods .................................. 139
4.4 Applications .......................................... 140
4.4.1 Ammonia Synthesis .............................. 141
4.4.2 Hydrotreating Reactions ........................ 143
4.4.3 Hydrogenation Reactions ........................ 147
4.5 Summary ............................................... 150
References ................................................. 150
5 Preparation of Carbon-Supported Metal Catalysts ............ 157
Johannes H. Bitter and Krijn P. de Jong
5.1 Introduction .......................................... 157
5.2 Impregnation and Adsorption ........................... 157
5.2.1 Interaction Between Support and Precursor ...... 158
5.2.2 Role of Pore Structure ......................... 164
5.3 Deposition Precipitation .............................. 165
5.3.1 Increase in pH ................................ 166
5.3.2 Change of Valency .............................. 169
5.3.3 Ligand Removal ................................. 170
5.4 Emerging Preparation Methods .......................... 171
5.5 Conclusions ........................................... 172
References ................................................. 173
6 Carbon as Catalyst ......................................... 177
José Luís Figueiredo and Manuel Fernando R. Pereira
6.1 Introduction .......................................... 177
6.2 Factors Affecting the Performance of a Carbon
Catalyst .............................................. 178
6.2.1 Nature of the Active Sites ..................... 178
6.2.2 Concentration of the Active Sites .............. 179
6.2.3 Accessibility of the Active Sites .............. 179
6.3 Reactions Catalyzed by Carbons ........................ 180
6.3.1 Oxidative Dehydrogenation ...................... 181
6.3.2 Dehydration of Alcohols ........................ 186
6.3.3 SOx Oxidation .................................. 188
6.3.4 NOx Reduction .................................. 190
6.3.5 H2S Oxidation .................................. 194
6.3.6 Hydrogen Peroxide Reactions .................... 196
6.3.7 Catalytic Ozonation ............................ 198
6.3.8 Catalytic Wet Air Oxidation .................... 203
6.3.9 Other Reactions ................................ 205
6.4 Conclusions ........................................... 207
References ................................................. 208
7 Catalytic Properties of Nitrogen-Containing Carbons ........ 219
Hanns-Peter Boehm
7.1 Introduction .......................................... 219
7.2 Nitrogen Doping of Carbons ............................ 220
7.2.1 Preparation of Nitrogen-Containing Carbons ..... 220
7.2.2 Quantitative Analysis .......................... 227
7.2.3 Electron Emission Spectrometric Analysis ....... 227
7.2.4 Properties of Nitrogen-Containing Carbons ...... 233
7.3 Catalysis of Oxidation Reactions with Dioxygen ........ 238
7.3.1 Oxidation of Aqueous Sulfurous Acid ............ 238
7.3.2 Oxidation of Oxalic Acid ....................... 244
7.3.3 Oxidation of Sulfur Dioxide .................... 244
7.3.4 Oxidation of Iron(II) Ions ..................... 246
7.3.5 Oxidation of Other Compounds ................... 247
7.4 Catalysis of Aging of Carbons ......................... 251
7.5 Catalysis of Dehydrochlorination Reactions ............ 254
7.6 Mechanism of Catalysis by Nitrogen-Containing
Carbons ............................................... 257
References ................................................. 259
8 Carbon-Anchored Metal Complex Catalysts .................... 267
Cristina Freire and Ana Rosa Silva
8.1 Introduction .......................................... 267
8.2 General Methods for Molecule Immobilization ........... 268
8.3 Methods for Immobilization of Transition-Metal
Complexes Onto Carbon Materials ....................... 270
8.3.1 Functionalization of Carbon Materials .......... 271
8.3.2 Direct Immobilization of Metal Complexes ....... 278
8.3.3 Metal Complex Immobilization via Spacers ....... 285
8.4 Application of Coordination Compounds Anchored Onto
Carbon Materials in Several Catalytic Reactions ....... 289
8.4.1 [M(salen)]-Based Materials ..................... 290
8.4.2 [M(acac)2]-Based Materials ..................... 293
8.4.3 Metal Phthalocyanine and Porphyrin-Based
Materials ...................................... 294
8.5 Application of Carbon-Supported Organometallic
Compounds in Hydrogenation and Hydroformylation
Catalytic Reactions ................................... 296
8.5.1 Materials Based on Pd and Rh Amino Complexes ... 296
8.5.2 Materials Based on Rh and Pd Complexes with
тт-Bonding Ligands (Phosphines and Dienes) ..... 297
8.6 Carbon-Supported Organometallic Complexes in the
Polymerization Reaction of Olefins .................... 300
8.7 Conclusions ........................................... 301
References ................................................. 302
9 Carbon Nanotubes and Nanofibers in Catalysis ............... 309
Philippe Serp
9.1 Introduction .......................................... 309
9.2 Catalytic Growth of Carbon Nanofibers and Nanotubes ... 312
9.2.1 Catalytic Carbon Deposition .................... 312
9.2.2 Growth Mechanism ............................... 313
9.3 Why CNTs or CNFs Can Be Suitable for Use in
Catalysis ............................................. 324
9.3.1 Structural Features and Electronic
Properties ..................................... 324
9.3.2 Adsorption Properties .......................... 328
9.3.3 Mechanical and Thermal Properties .............. 330
9.3.4 Macroscopic Shaping of CNTs and CNFs ........... 331
9.4 Preparation of Supported Catalysts on CNTs and CNFs ... 333
9.5 Catalytic Performance of CNT- and CNF-Based
Catalysts ............................................. 340
9.5.1 Hydrogenation Reactions ........................ 340
9.5.2 Reactions Involving CO/H2 ...................... 344
9.5.3 Polymerization ................................. 345
9.5.4 Carbon Nanotubes Synthesis by Catalytic
Decomposition of Hydrocarbons .................. 348
9.5.5 Ammonia Synthesis and Decomposition ............ 349
9.5.6 Environmental Catalysis and Oxidation
Reactions ...................................... 350
9.5.7 Other Reactions ................................ 351
9.5.8 Fuel Cell Electrocatalysts ..................... 354
9.5.9 CNTs for Enzyme Immobilization ................. 355
9.5.10 CNTs and CNFs as Catalysts ..................... 356
9.6 Conclusions ........................................... 356
References ................................................. 358
10 Carbon Gels in Catalysis ................................... 373
Carlos Moreno-Castilla
10.1 Introduction .......................................... 373
10.2 Carbon Gels: Preparation and Surface Properties ....... 374
10.3 Metal-Doped Carbon Gels ............................... 376
10.3.1 Dissolving the Metal Precursor in the Initial
Mixture ........................................ 378
10.3.2 Introducing a Functionalized Moiety ............ 381
10.3.3 Depositing the Metal Precursor on the Organic
or Carbon Gel .................................. 382
10.4 Catalytic Reactions of Metal-Doped Carbon Gels ........ 383
10.4.1 Environmental Applications ..................... 384
10.4.2 Fuel Cell Applications ......................... 387
10.4.3 C=C Double-Bond Hydrogenation .................. 389
10.4.4 Skeletal Isomerization of 1-Butene ............. 391
10.4.5 Hydrodechlorination Reaction ................... 392
10.4.6 Other Reactions ................................ 392
10.5 Conclusions ........................................... 393
References ................................................. 395
11 Carbon Monoliths in Catalysis .............................. 401
Karen M. de Lathouder, Edwin Crezee, Freek Kapteijn,
and Jacob A. Moulijn
11.1 Introduction .......................................... 401
11.2 Carbon ................................................ 401
11.3 Monolithic Structures ................................. 402
11.4 Carbon Monoliths ...................................... 402
11.5 Carbon Monoliths in Catalysis: An Overview ............ 404
11.6 Example of Carbon Monoliths as Catalyst Support
Material .............................................. 405
11.6.1 Carbon Monoliths as Support Material in
Biocatalysis ................................... 405
11.6.2 Selective Hydrogenation of D-Glucose over
Monolithic Ruthenium Catalysts ................. 405
11.6.3 Performance of Carbon Monoliths ................ 406
11.6.4 Morphology and Porosity of Various Carbon
Composites ..................................... 407
11.6.5 Enzyme Adsorption and Catalyst Performance in
the MSR ........................................ 413
11.6.6 Performance of Monolithic Ruthenium
Catalysts ...................................... 416
11.7 Evaluation and Practical Considerations ............... 420
11.7.1 Monolithic Biocatalysts ........................ 420
11.7.2 Monolithic Ruthenium Catalysts ................. 421
11.7.3 Practical Considerations ....................... 421
11.8 Conclusions ........................................... 423
References ................................................. 424
12 Carbon Materials as Supports for Fuel Cell
Electrocatalysts ........................................... 429
Frédéric Maillard, Pavel A. Simonov, and Elena
R. Savinova
12.1 Introduction .......................................... 429
12.2 Structure and Morphology of Carbon Materials .......... 433
12.2.1 Carbon Blacks .................................. 433
12.2.2 Activated Carbons .............................. 434
12.2.3 Carbons of the Sibunit Family .................. 435
12.2.4 Ordered Mesoporous Carbons ..................... 436
12.2.5 Carbon Aerogels ................................ 436
12.2.6 Carbon Nanotubes and Nanofibers ................ 437
12.3 Physicochemical Properties of Carbon Materials
Relevant to Fuel Cell Operation ....................... 438
12.3.1 Electron Conduction ............................ 438
12.3.2 Surface Properties ............................. 440
12.4 Preparation of Carbon-Supported Electrocatalysts ...... 443
12.4.1 Methods Based on Impregnation .................. 444
12.4.2 Colloidal Synthesis ............................ 445
12.4.3 Electrodeposition .............................. 445
12.4.4 Other Methods .................................. 446
12.5 Structural Characterization of Carbon-Supported
Metal Catalysts ....................................... 446
12.5.1 Adsorption Studies ............................. 447
12.5.2 Transmission Electron Microscopy ............... 448
12.5.3 Xray Diffraction and Xray Absorption
Spectroscopy ................................... 449
12.5.4 Electrochemical Methods ........................ 450
12.6 Influence of Carbon Supports on the Catalytic Layers
in PEMFCs ............................................. 452
12.6.1 Intrinsic Catalytic Activity ................... 452
12.6.2 Macrokinetic Parameters ........................ 456
12.6.3 Novel Carbon Materials as Supports for Fuel
Cell Electrocatalysts .......................... 462
12.7 Corrosion and Stability of Carbon-Supported
Catalysts ............................................. 464
12.7.1 Influence of Microstructure on the Corrosion
of Carbon Materials ............................ 464
12.7.2 Mechanism of Carbon Corrosion .................. 466
12.7.3 Corrosion and Stability of MEAs ................ 467
12.8 Conclusions .......................................... 469
References ................................................. 470
13 Carbon Materials in Photocatalysis
Joaquim Luís Faria and Wendong Wang
13.1 Introduction .......................................... 481
13.2 Carbon Materials Employed to Modify ТiO2 in
Photocatalysis ........................................ 482
13.2.1 Activated Carbon ............................... 482
13.2.2 Carbon Black and Graphite ...................... 483
13.2.3 Carbon Fiber ................................... 483
13.2.4 Carbon Nanotubes ............................... 483
13.2.5 Other Forms of Carbon .......................... 484
13.3 Synthesis and Characterization of Carbon-TiO2
Composites ............................................ 484
13.3.1 Mechanical Mixture of ТiO2 and Carbon
Materials ...................................... 485
13.3.2 ТiO2 Coated or Loaded on Carbon Materials ...... 485
13.3.3 Carbon Materials Coated or Deposited on ТiO2 ... 485
13.3.4 Other Approaches and Concurrent Synthesis of
ТiO2-Carbon Composites ......................... 486
13.3.5 Methods of Characterization .................... 486
13.4 Photodegradation on Carbon-Containing Surfaces ........ 487
13.4.1 Heterogeneous Photocatalysis in the Liquid
Phase with Carbon-TiO2 Composites .............. 487
13.4.2 Heterogeneous Photocatalysis in the Gas Phase
with Carbon-TiO2 Composites .................... 491
13.5 Role of the Carbon Phase in Heterogeneous
Photocatalysis ........................................ 492
13.6 Conclusions ........................................... 498
References ............................................ 499
14 Carbon-Based Sensors ....................................... 507
Jim Li
14.1 Introduction .......................................... 507
14.1.1 Structure of Various Carbon Allotropes ......... 507
14.1.2 sp2 Carbon Materials: Graphite, Fullerenes,
and Carbon Nanotubes ........................... 509
14.2 Physicochemical Properties of sp2 Carbon Materials
Relevant to Carbon Sensors ............................ 510
14.2.1 Electrical and Electronic Properties ........... 510
14.2.2 Chemical Properties ............................ 515
14.2.3 Electrochemical Properties ..................... 516
14.3 Carbon-Based Sensors .................................. 517
14.3.1 Carbon Materials as Loading Media .............. 518
14.3.2 Carbon Electronic Sensors ...................... 518
14.3.3 Carbon Electrochemical Sensors ................. 523
14.3.4 Carbon Composite Sensors ....................... 530
14.4 Summary ............................................... 530
References ................................................. 530
15 Carbon-Supported Catalysts for the Chemical Industry ....... 535
Venu Arunajatesan, Baoshu Chen, Konrad Möbus, Daniel J.
Ostgard, Thomas Tacke, and Dorit Wolf
15.1 Introduction .......................................... 535
15.2 Requirements for Carbon Materials as Catalyst
Supports in Industrial Applications ................... 536
15.2.1 Activated Carbon ............................... 536
15.2.2 Carbon Black ................................... 540
15.3 Industrial Manufacture of Carbon Supports ........ 544
15.3.1 Activated Carbon ............................... 544
15.3.2 Carbon Black ................................... 544
15.4 Manufacture of Carbon-Supported Catalysts ............. 545
15.4.1 Powder Catalysts ............................... 545
15.4.2 Preparation Technology ......................... 547
15.5 Reaction Technology ................................... 547
15.5.1 Batch Stirred-Tank and Loop Reactors ........... 548
15.5.2 Fixed-Bed Reactors ............................. 550
15.6 Industrial Applications ............................... 551
15.6.1 Fatty Acid Hydrogenation ....................... 551
15.6.2 Selective Nitrobenzene Hydrogenations .......... 554
15.6.3 Reductive Alkylation ........................... 555
15.6.4 Toluenediamine ................................. 556
15.6.5 Butanediol ..................................... 558
15.6.6 Purified Terephthalic Acid ..................... 560
15.7 Testing and Evaluation of Carbon Catalyst ............ 561
15.7.1 Current Methods for Catalyst Evaluation ........ 561
15.7.2 High-Throughput Testing of Carbon Powder
Catalysts ...................................... 563
15.7.3 Catalyst Profiling ............................. 565
15.8 Conclusions ........................................... 567
References ................................................. 568
Index ......................................................... 573
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