The Development of Catalysis

Preface ix
1 From the Onset to the First Large-Scale Industrial Processes 1
1.1 Origin of the Catalytic Era 1
1.2 Berzelius and the Affinity Theory of Catalysis 4
1.3 Discovery of the Occurrence of Catalytic Processes in Living Systems in the Nineteenth Century 6
1.4 Kinetic Interpretation of Catalytic Processes in Solutions: The Birth of Homogeneous Catalysis 8
1.5 Onset of Heterogeneous Catalysis 18
1.6 First Large-Scale Industrial Processes Based on Heterogeneous Catalysts 26
1.6.1 Sulfuric Acid Synthesis 26
1.6.2 Ammonia Problem 29
1.6.3 Ammonia Oxidation Process 32
1.6.4 Ammonia Synthesis 33
1.7 Fischer-Tropsch Catalytic Process 40
1.8 Methanol Synthesis 44
1.9 Acetylene Production and Utilization 46
1.10 Anthraquinone Process for Hydrogen Peroxide Production 47
References 49
2 Historical Development of Theories of Catalysis 59
2.1 Heterogeneous Catalysis 59
2.2 Chemical Kinetics and the Mechanisms of Catalysis 62
2.3 Electronic Theory of Catalysis: Active Sites 72
References 76
3 Catalytic Processes Associated with Hydrocarbons and the Petroleum Industry 83
3.1 Petroleum and Polymer Eras 83
3.2 Catalytic Cracking, Isomerization, and Alkylation of Petroleum Fractions 84
3.3 Reforming Catalysts 91
3.4 Hydrodesulfurization (HDS) Processes 93
3.5 Hydrocarbon Hydrogenation Reactions with Heterogeneous Catalysts 94
3.6 Olefin Polymerization: Ziegler-Natta, Metallocenes, and Phillips Catalysts 98
3.7 Selective Oxidation Reactions 109
3.7.1 Alkane Oxidation 109
3.7.2 Olefin Oxidation 110
3.7.3 Aromatic Compounds Oxidation 111
3.8 Ammoximation and Oxychlorination of Olefins 113
3.9 Ethylbenzene and Styrene Catalytic Synthesis 117
3.10 Heterogeneous Metathesis 118
3.11 Catalytic Synthesis of Carbon Nanotubes and Graphene from Hydrocarbon Feedstocks 119
References 121
4 Surface Science Methods in the Second Half of the Twentieth Century 131
4.1 Real Dispersed Catalysts versus Single Crystals: A Decreasing Gap 131
4.2 Physical Methods for the Study of Dispersed Systems and Real Catalysts 132
4.3 Surface Science of Single-Crystal Faces and of Well-defined Systems 139
References 147
5 Development of Homogeneous Catalysis and Organocatalysis 155
5.1 Introductory Remarks 155
5.2 Homogeneous Acid and Bases as Catalysts: G. Olah Contribution 156
5.3 Organometallic Catalysts 161
5.4 Asymmetric Epoxidation Catalysts 175
5.5 Olefin Oligomerization Catalysts 179
5.6 Organometallic Metathesis 180
5.7 Cross-Coupling Reactions 186
5.8 Pd(II)-Based Complexes and Oxidation of Methane to Methanol 190
5.9 Non-transition Metal Catalysis, Organocatalysis, and Organo-Organometallic Catalysis Combination 191
5.9.1 Metal-Free Hydrogen Activation and Hydrogenation 192
5.9.2 Amino Catalysis 193
5.10 Bio-inspired Homogeneous Catalysts 194
References 195
6 Material Science and Catalysis Design 205
6.1 Metallic Catalysts 205
6.2 Oxides and Mixed Oxides 208
6.2.1 SiO2 and SiO2-Based Catalysts and Processes 209
6.2.2 Al2O3 and Al2O3-Based Catalysts and Processes 211
6.2.3 SiO2-Al2O3. and SiO2-Al2O3-Based Catalysts and Processes 211
6.2.4 MgO. and MgO-Based Catalysts and Processes 212
6.2.5 ZrO2 and ZrO2-Based Catalysts and Processes 212
6.3 Design of Catalysts with Shape and Transition-State Selectivity 213
6.4 Zeolites and Zeolitic Materials: Historical Details 214
6.5 Zeolites and Zeolitic Materials Structure 218
6.6 Shape-Selective Reactions Catalyzed by Zeolites and Zeolitic Materials 221
6.6.1 Alkanes- and Alkene-Cracking and Isomerization 222
6.6.2 Aromatic Ring Positional Isomerizations 223
6.6.3 Synthesis of Ethyl Benzene, Cumene, and Alkylation of Aromatic Molecules 224
6.6.4 Friedel-Crafts Acylation of Aromatic Molecules 225
6.6.5 Toluene Alkylation with Methanol 225
6.6.6 Asaki Process for Cyclohexanol Synthesis 226
6.6.7 Methanol-to-Olefins (MTO) Process 226
6.6.8 Nitto Process 227
6.6.9 Butylamine Synthesis 227
6.6.10 Beckman Rearrangements on Silicalite Catalyst 227
6.6.11 Partial Oxidation Reactions Using Titanium Silicalite 227
6.6.12 Nylon-6 Synthesis: The Role of Zeolitic Catalysts 229
6.6.13 Pharmaceutical Product Synthesis 229
6.7 Organic-Inorganic Hybrid Zeolitic Materials and Inorganic Microporous Solids 230
6.7.1 Organic-Inorganic Hybrid Zeolitic Materials 230
6.7.2 ETS-10: A Microporous Material Containing Monodimensional TiO2 Chains 231
6.7.3 Hydrotalcites: Microporous Solids with Exchangeable Anions 232
6.8 Microporous Polymers and Metal-Organic Frameworks (MOFs) 232
6.8.1 Microporous Polymers 232
6.8.2 Metal-organic Frameworks 234
References 235
7 Photocatalysis 243
7.1 Photochemistry and Photocatalysis: Interwoven Branches of Science 243
7.2 Photochemistry Onset 245
7.3 Physical Methods in Photochemistry 249
7.4 Heterogeneous and Homogeneous Photocatalysis 251
7.5 Natural Photosynthesis as Model of Photocatalysis 253
7.6 Water Splitting, CO2 Reduction, and Pollutant Degradation: The Most Investigated Artificial Photocatalytic Processes 256
7.6.1 Water Splitting 257
7.6.2 CO2 Photoreduction 261
7.6.3 Photocatalysis in Environmental Protection 263
References 264
8 Enzymatic Catalysis 269
8.1 Early History of Enzymes 269
8.2 Proteins and Their Role in Enzymatic Catalysis 273
8.3 Enzymes/Coenzymes Structure and Catalytic Activity 284
8.4 Mechanism of Enzyme Catalysis 288
8.5 Biocatalysis 294
References 295
9 Miscellanea 299
9.1 Heterogeneous and Homogeneous Catalysis in Prebiotic Chemistry 299
9.2 Opportunities for Catalysis in the Twenty-First Century and the
Green Chemistry 312
References 317
Index 321