Catalysis An Integrated Textbook for Students

Written by an excellent, highly experienced and motivated team of lecturers, this textbook is based on one of the most successful courses in catalysis and as such is tried-and-tested by generations of graduate and PhD students, i.e. the Catalysis-An-Integrated-Approach (CAIA) course organized by NIOK, the Dutch Catalysis research school.
It covers all essential aspects of this important topic, including homogeneous, heterogeneous and biocatalysis, but also kinetics, catalyst characterization and preparation, reactor design and engineering.
The perfect source of information for graduate and PhD students in chemistry and chemical engineering, as well as for scientists wanting to refresh their knowledge

Ulf Hanefeld is Professor of Biocatalysis at the Department of Biotechnology at Delft University of Technology, The Netherlands. His research focuses on the hydroxynitrile lyase enzymes, heterogeneous catalysis combined with biocatalysis, and more broadly on the catalytic formation of carbon-carbon bonds. Besides his extensive research portfolio, Hanefeld is an important figurehead for education in biocatalysis.

Leon Lefferts was appointed Professor at Twente University in 1999, after having worked at the industrial laboratories of DSM for 12 years. He has been visiting professor at both Tokyo Institute of Technology, 2005?2007, as well at at Aalto University in Helsinki since 2011. His research interests are within the field of applied heterogeneous catalysis, with emphasis on activation of stable molecules, e.g. methane, carbon dioxide and water, heterogeneous catalyst in gas-liquid systems as well as catalytic upgrading of biomass based feeds, e.g. flash pyrolysis oil.

Preface xiii

1 Introduction 1
Leon Lefferts, Ulf Hanefeld, and Harry Bitter

1.1 A FewWords at the Beginning 1

1.2 Catalysis in a Nutshell 1

1.3 History of Catalysis 3

1.3.1 Industrial Catalysis 4

1.3.2 Environmental Catalysis 5

1.4 Integration Homo–Hetero-Biocatalysis 5

1.5 Research in Catalysis 10

1.5.1 S-Curve, Old Processes Improvement Is Knowledge Intensive 10

1.5.2 Interdependence with Other Fields 11

1.5.3 Recent and Future Issues 12

1.6 Catalysis and Integrated Approach or How to Use this Book 14

References 14

2 Heterogeneous Catalysis 15
Leon Lefferts, Emiel Hensen, and Hans Niemantsverdriet

2.1 Introduction 15

2.1.1 Concept of Heterogeneous Catalysis 15

2.1.2 Applications of Heterogeneous Catalysis 16

2.1.3 Catalytic Cycle 23

2.2 Adsorption on Surfaces 23

2.2.1 Physisorption and Chemisorption 24

2.2.2 Adsorption Isotherms 26

2.2.3 Chemisorption and Chemical Bonding 28

2.2.4 Connecting Kinetic andThermodynamic Formulations 33

2.3 Surface Reactions 35

2.3.1 Reaction Mechanism and Kinetics 35

2.4 Types of Heterogeneous Catalysts 41

2.4.1 Supported Metals 41

2.4.2 Oxides and Sulfides 51

2.4.3 Solid Acid Catalysts 62

Question 1 69

Question 2 69

References 70

3 Homogeneous Catalysis 73
Elisabeth Bouwman,Martin C. Feiters, and Robertus J. M. Klein Gebbink

3.1 Framework and Outline 73

3.1.1 Outline of this Chapter 73

3.1.2 Definitions and Terminology 74

3.2 Coordination and Organometallic Chemistry 75

3.2.1 Coordination Chemistry: d Orbitals, Geometries, Crystal Field Theory 75

3.2.2 σ and π donors and back-donation: CO, alkene, phosphane, H2 77

3.2.3 Organometallics: Hapticity, Metal–Alkyl/Allyl, Agostic Interaction, Carbenes 80

3.2.4 Electron Counting: Ionogenic or Donor-Pair versus Covalent or Neutral-Ligand 81

3.2.5 Effect of Binding on Ligands andMetal Ions, Stabilization of Oxidation States 83

3.3 Elementary Steps in Homogeneous Catalysis 84

3.3.1 Formation of the Active Catalyst Species 84

3.3.2 Oxidative Addition and Reductive Elimination 85

3.3.3 Migration and Elimination 87

3.3.4 Oxidative Coupling and Reductive Cleavage 90

3.3.5 Alkene or Alkyne Metathesis and σ-Bond Metathesis 90

3.3.6 Nucleophilic and Electrophilic Attack 92

3.4 Homogeneous Hydrogenation 95

3.4.1 Background and Scope 95

3.4.2 H2 DihydrideMechanism:Wilkinson’s Catalyst 96

3.4.3 H2 Monohydride Mechanism and Heterolytic Cleavage 97

3.4.4 Asymmetric Homogeneous Hydrogenation 98

3.4.5 Transfer Hydrogenation with 2-Propanol 100

3.4.6 Other Alkene Addition Reactions 102

3.5 Hydroformylation 104

3.5.1 Scope and Importance of the Reaction and Its Products 104

3.5.2 Cobalt-Catalyzed Hydroformylation 105

3.5.3 Rhodium-Catalyzed Hydroformylation 107

3.5.4 Asymmetric Hydroformylation 110

3.6 Oligomerization and Polymerization of Alkenes 112

3.6.1 Scope and Importance of Oligomerization and Polymerization 112

3.6.2 Oligomerization of Ethene (Ni, Cr) 113

3.6.3 Stereochemistry and Mechanism of Propene Polymerization 115

3.6.4 Metallocene Catalysis 117

3.6.5 Polymerization with Non-Metallocenes (Pd, Ni, Fe, Co) 118

3.7 Miscellaneous Homogeneously Catalyzed Reactions 118

3.7.1 Cross-Coupling Reactions: Pd-Catalyzed C–C Bond Formation 118

3.7.2 Metathesis Reactions 120

Question 1 (total 20 points) 122

Question 2 (total 20 points) 122

References 123

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Catalysis An Integrated Textbook for Students

Summary

Author Biography

Table of Contents

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Catalysis An Integrated Textbook for Students

Summary

Author Biography

Table of Contents

Supplemental Materials

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