Development of Catalysis

Adriano Zecchina, Ph.D, is Professor Emeritus of the University of Turin, where he was full professor of physical chemistry from 1975 to 2009. He is a member of the National Academy of Lincei and Academia Europaea. His research is mainly devoted to studying the surface properties of catalytic materials with spectroscopic methods. Salvatore Califano, Ph.D, is the director of the European Laboratory of Molecular Spectroscopy in Florence, Italy. His main research focuses on dynamics of molecular crystals and determination of the lifetime of phonons and vibrons by pico- and femtosecond spectroscopy or by high-resolution infrared and Raman spectroscopy.

• Preface ix1 From the Onset to the First Large-Scale Industrial Processes 11.1 Origin of the Catalytic Era 11.2 Berzelius and the Affinity Theory of Catalysis 41.3 Discovery of the Occurrence of Catalytic Processes in Living Systems in the Nineteenth Century 61.4 Kinetic Interpretation of Catalytic Processes in Solutions: The Birth of Homogeneous Catalysis 81.5 Onset of Heterogeneous Catalysis 181.6 First Large-Scale Industrial Processes Based on Heterogeneous Catalysts 261.6.1 Sulfuric Acid Synthesis 261.6.2 Ammonia Problem 291.6.3 Ammonia Oxidation Process 321.6.4 Ammonia Synthesis 331.7 Fischer–Tropsch Catalytic Process 401.8 Methanol Synthesis 441.9 Acetylene Production and Utilization 461.10 Anthraquinone Process for Hydrogen Peroxide Production 47References 492 Historical Development of Theories of Catalysis 592.1 Heterogeneous Catalysis 592.2 Chemical Kinetics and the Mechanisms of Catalysis 622.3 Electronic Theory of Catalysis: Active Sites 72References 763 Catalytic Processes Associated with Hydrocarbons and the Petroleum Industry 833.1 Petroleum and Polymer Eras 833.2 Catalytic Cracking, Isomerization, and Alkylation of Petroleum Fractions 843.3 Reforming Catalysts 913.4 Hydrodesulfurization (HDS) Processes 933.5 Hydrocarbon Hydrogenation Reactions with Heterogeneous Catalysts 943.6 Olefin Polymerization: Ziegler–Natta, Metallocenes, and Phillips Catalysts 983.7 Selective Oxidation Reactions 1093.7.1 Alkane Oxidation 1093.7.2 Olefin Oxidation 1103.7.3 Aromatic Compounds Oxidation 1113.8 Ammoximation and Oxychlorination of Olefins 1133.9 Ethylbenzene and Styrene Catalytic Synthesis 1173.10 Heterogeneous Metathesis 1183.11 Catalytic Synthesis of Carbon Nanotubes and Graphene from Hydrocarbon Feedstocks 119References 1214 Surface Science Methods in the Second Half of the Twentieth Century 1314.1 Real Dispersed Catalysts versus Single Crystals: A Decreasing Gap 1314.2 Physical Methods for the Study of Dispersed Systems and Real Catalysts 1324.3 Surface Science of Single-Crystal Faces and of Well-defined Systems 139References 1475 Development of Homogeneous Catalysis and Organocatalysis 1555.1 Introductory Remarks 1555.2 Homogeneous Acid and Bases as Catalysts: G. Olah Contribution 1565.3 Organometallic Catalysts 1615.4 Asymmetric Epoxidation Catalysts 1755.5 Olefin Oligomerization Catalysts 1795.6 Organometallic Metathesis 1805.7 Cross-Coupling Reactions 1865.8 Pd(II)-Based Complexes and Oxidation of Methane to Methanol 1905.9 Non-transition Metal Catalysis, Organocatalysis, and Organo-Organometallic Catalysis Combination 1915.9.1 Metal-Free Hydrogen Activation and Hydrogenation 1925.9.2 Amino Catalysis 1935.10 Bio-inspired Homogeneous Catalysts 194References 1956 Material Science and Catalysis Design 2056.1 Metallic Catalysts 2056.2 Oxides and Mixed Oxides 2086.2.1 SiO2 and SiO2-Based Catalysts and Processes 2096.2.2 Al2O3 and Al2O3-Based Catalysts and Processes 2116.2.3 SiO2–Al2O3− and SiO2–Al2O3-Based Catalysts and Processes 2116.2.4 MgO− and MgO-Based Catalysts and Processes 2126.2.5 ZrO2 and ZrO2-Based Catalysts and Processes 2126.3 Design of Catalysts with Shape and Transition-State Selectivity 2136.4 Zeolites and Zeolitic Materials: Historical Details 2146.5 Zeolites and Zeolitic Materials Structure 2186.6 Shape-Selective Reactions Catalyzed by Zeolites and Zeolitic Materials 2216.6.1 Alkanes- and Alkene-Cracking and Isomerization 2226.6.2 Aromatic Ring Positional Isomerizations 2236.6.3 Synthesis of Ethyl Benzene, Cumene, and Alkylation of Aromatic Molecules 2246.6.4 Friedel–Crafts Acylation of Aromatic Molecules 2256.6.5 Toluene Alkylation with Methanol 2256.6.6 Asaki Process for Cyclohexanol Synthesis 2266.6.7 Methanol-to-Olefins (MTO) Process 2266.6.8 Nitto Process 2276.6.9 Butylamine Synthesis 2276.6.10 Beckman Rearrangements on Silicalite Catalyst 2276.6.11 Partial Oxidation Reactions Using Titanium Silicalite 2276.6.12 Nylon-6 Synthesis: The Role of Zeolitic Catalysts 2296.6.13 Pharmaceutical Product Synthesis 2296.7 Organic–Inorganic Hybrid Zeolitic Materials and Inorganic Microporous Solids 2306.7.1 Organic–Inorganic Hybrid Zeolitic Materials 2306.7.2 ETS-10: A Microporous Material Containing Monodimensional TiO2 Chains 2316.7.3 Hydrotalcites: Microporous Solids with Exchangeable Anions 2326.8 Microporous Polymers and Metal–Organic Frameworks (MOFs) 2326.8.1 Microporous Polymers 2326.8.2 Metal–organic Frameworks 234References 2357 Photocatalysis 2437.1 Photochemistry and Photocatalysis: Interwoven Branches of Science 2437.2 Photochemistry Onset 2457.3 Physical Methods in Photochemistry 2497.4 Heterogeneous and Homogeneous Photocatalysis 2517.5 Natural Photosynthesis as Model of Photocatalysis 2537.6 Water Splitting, CO2 Reduction, and Pollutant Degradation: The Most Investigated Artificial Photocatalytic Processes 2567.6.1 Water Splitting 2577.6.2 CO2 Photoreduction 2617.6.3 Photocatalysis in Environmental Protection 263References 2648 Enzymatic Catalysis 2698.1 Early History of Enzymes 2698.2 Proteins and Their Role in Enzymatic Catalysis 2738.3 Enzymes/Coenzymes Structure and Catalytic Activity 2848.4 Mechanism of Enzyme Catalysis 2888.5 Biocatalysis 294References 2959 Miscellanea 2999.1 Heterogeneous and Homogeneous Catalysis in Prebiotic Chemistry 2999.2 Opportunities for Catalysis in the Twenty-First Century and theGreen Chemistry 312References 317Index 321