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. Nanostructure 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 NO_x, 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. SO_x Oxidation 188

6.3.4. NO_x 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 π-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 481
Joaquim Luís Faria and Wendong Wang

13.1. Introduction 481

13.2. Carbon Materials Employed to Modify TiO₂ 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 TiO₂ and Carbon Materials 485

13.3.2. TiO₂ Coated or Loaded on Carbon Materials 485

13.3.3. Carbon Materials Coated or Deposited on TiO₂ 485

13.3.4. Other Approaches and Concurrent Synthesis of TiO₂–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
Jun 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 Catalysts 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