Catalysis: An Integrated Textbook for Students

ISBN-13: 9783527341597 / Angielski / Miękka / 2018 / 384 str.

Hanefeld, Ulf

Opis

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.
It covers all essential aspects of this important topic, including homogeneous, heterogeneous and biocatalysis, but also kinetics, 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.

Tried–and–tested by generations of graduate and PhD students in chemistry and chemical engineering and based on one of the most successful catalysis courses: This is the perfect catalysis textbook. Covering every aspects like biocatalysis, reactor design, kinetics and much morer.

Spis treści

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 and 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 –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

Further Reading 124

4 Biocatalysis 127
Guzman Torrelo, Frank Hollmann, and Ulf Hanefeld

4.1 Introduction 127

4.2 Why Are Enzymes So Huge? 129

4.3 Classification of Enzymes 137

4.3.1 Oxidoreductases (EC 1) 139

4.3.2 Transferases (EC 2) 147

4.3.3 Hydrolases (EC 3) 147

4.3.4 Lyases (EC 4) 157

4.4 Concepts and Methods 157

4.4.1 Cofactor Regeneration Systems 158

4.4.2 Methods to Shift Unfavorable Equilibria 159

4.4.3 Two–Liquid–Phase Systems (and Related) 164

4.4.4 (Dynamic) Kinetic Resolutions and Desymmetrization 164

4.4.5 Enantiomeric Ratio E 168

4.5 Applications and Case Studies 169

4.5.1 Oxidoreductases (E.C. 1) 169

4.5.2 Transferases (EC 2) 177

4.5.3 Hydrolases (EC 3) 179

4.5.3.1 Lipases and Esterases (EC 3.1.1) 179

4.5.4 Lyases (EC 4) 181

Question 1 186

Question 2 186

Question 3 187

Question 4 188

Further Reading 188

5 Chemical Kinetics of Catalyzed Reactions 191
Freek Kapteijn, Jorge Gascon, and T. Alexander Nijhuis

5.1 Introduction 191

5.2 Rate Expressions Quasi–Steady–State Approximation and Quasi–Equilibrium Assumption 193

5.3 Adsorption Isotherms 198

5.3.1 One–Component Adsorption 198

5.3.2 Multicomponent Adsorption 199

5.3.3 Dissociative Adsorption 200

5.4 Rate Expressions Other Models and Generalizations 200

5.5 Limiting Cases Reactant and Product Concentrations 202

5.6 Temperature and Pressure Dependence 206

5.6.1 Transition–StateTheory 207

5.6.2 Forward Reaction Temperature and Pressure Dependence 208

5.6.3 Forward Reaction Limiting Cases 209

5.7 Sabatier Principle Volcano Plot 213

5.8 Concluding Remarks 214

Notation 216

Greek 217

Subscripts 217

Superscripts 217

Question 1 217

Question 2 218

Question 3 218

References 219

6 Catalytic Reaction Engineering 221
Freek Kapteijn, Jorge Gascon, and T. Alexander Nijhuis

6.1 Introduction 221

6.2 Chemical Reactors 222

6.2.1 Balance and Definitions 222

6.2.2 Batch Reactor 224

6.2.2.1 Multiple Reactions 226

6.2.3 Continuous Flow Stirred Tank Reactor (CSTR) 228

6.2.4 Plug–Flow Reactor (PFR) 231

6.2.5 Comparison between Plug–flow and CSTR reactor 233

6.3 Reaction and Mass Transport 236

6.3.1 External Mass Transfer 237

6.3.2 Internal Mass Transport 242

6.3.3 Gas Liquid Mass Transfer 248

6.3.4 Heat Transfer 254

6.4 Criteria to Check for Transport Limitations 257

6.4.1 Numerical Checks 257

6.4.2 Experimental Checks 260

Notation 264

Greek symbols 265

Subscripts 265

Question 1 265

Question 2 266

Question 3 267

References 269

7 Characterization of Catalysts 271
Guido Mul, Frank de Groot, Barbara Mojet–Mol, and Moniek Tromp

7.1 Introduction 271

7.1.1 Importance of Characterization of Catalysts 271

7.1.2 Overview of the Various Techniques 271

7.2 Techniques Based on Probe Molecules 273

7.2.1 Temperature–Programmed Techniques 273

7.2.2 Physisorption and Chemisorption 275

7.3 Electron Microscopy Techniques 280

7.4 Techniques from Ultraviolet up to Infrared Radiation 283

7.4.1 UV/Vis Spectroscopy 283

7.4.2 Infrared Spectroscopy 286

7.4.3 Raman Spectroscopy 289

7.5 Techniques Based on X–Rays 291

7.5.1 Introduction 291

7.5.2 Interaction of X–Rays with Matter 293

7.5.3 X–Ray Photoelectron Spectroscopy (XPS) 294

7.5.4 X–ray Absorption Spectroscopy (XAS) 295

7.5.5 X–Ray Scattering 299

7.5.6 X–Ray Microscopy 302

7.6 Ion Spectroscopies 303

7.7 Magnetic Resonance Spectroscopy Techniques 304

7.7.1 NMR 304

7.7.2 EPR 306

7.8 Summary 310

Question 1 310

Question 2 311

Question 3 312

References 313

8 Synthesis of Solid Supports and Catalysts 315
Petra de Jongh and Krijn de Jong

8.1 Introduction 315

8.2 Support Materials 317

8.2.1 Mesoporous Metal Oxides 318

8.2.2 Ordered Microporous Materials 326

8.2.3 Carbon Materials 331

8.2.4 Shaping 333

8.3 Synthesis of Supported Catalysts 333

8.3.1 Colloidal Synthesis Routes 334

8.3.2 Chemical Vapor Deposition 335

8.3.3 Ion Adsorption 338

8.3.4 Deposition Precipitation 341

8.3.5 Co–Precipitation 345

8.3.6 Impregnation and Drying 349

Question 1 357

Question 2 357

Question 3 358

References 358

Index 361

O autorze

Prof. 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 is Professor at Twente University. He is member of the board of NIOK and had several functions including chairman of the board of the Catalysis Section of the Royal Dutch Chemical Society. He has been visiting professor at Tokyo Institute of Technology, 2005–2007. He acted as director of the research institute IMPACT (2010–2011) and the Green Energy Initiative (2013–) at the University of Twente. He was appointed as a Finnish Distinguished Professor in 2011 as a visiting professor at Aalto University in Helsinki. His research interests within the field of applied heterogeneous catalysis.