Edited by

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Bridging Heterogeneous andHomogeneous Catalysis

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Edited by Can Li and Yan Liu

Bridging Heterogeneous and HomogeneousCatalysis

Concepts, Strategies, and Applications

Editors

Dr. Can LiChinese Academy of SciencesState Key Laboratory of CatalysisDalian Institute of Chemical Physics457, Zhongshan RoadDalian 116023China

Dr. Yan LiuChinese Academy of SciencesState Key Laboratory of CatalysisDalian Institute of Chemical Physics457, Zhongshan RoadDalian 116023China

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V

Contents

Preface XVList of Contributors XIX

1 Acid–Base Cooperative Catalysis for Organic Reactions by DesignedSolid Surfaces with Organofunctional Groups 1Ken Motokura, Toshihide Baba, and Yasuhiro Iwasawa

1.1 Introduction 1

1.2 Bifunctional Catalysts Possessing Both Acidic and Basic OrganicGroups 2

1.2.1 Urea–Amine Bifunctional Catalyst 2

1.2.2 Sulfonic or Carboxylic Acid–Amine Bifunctional Catalyst 3

1.3 Bifunctional Catalysts Possessing Basic Organic Groups and AcidSites Derived from Their Support Surface 7

1.3.1 Organic Base-Catalyzed Reactions Enhanced by SiO2 7

1.3.2 Amine-Catalyzed Reactions Enhanced by Acid Site onSilica–Alumina 11

1.3.3 Control of Acid–Base Interaction on Solid Surface 13

1.3.4 Cooperative Catalysis of Acid Site, Primary Amine, and TertiaryAmine 18

1.4 Prospect 19

References 20

2 Catalytic Reactions in or by Room-Temperature Ionic Liquids: Bridgingthe Gap between Homogeneous and Heterogeneous Catalysis 21Youquan Deng, Feng Shi, and Qinghua Zhang

2.1 Introduction and Background 21

2.2 Catalysis with IL-Supported or Mediated Metal Nanoparticles 22

2.2.1 Preparation of MNPs in ILs 23

2.2.1.1 IL Itself as the Reducing Agent 24

2.2.1.2 Molecular Hydrogen as Reducing Agent 24

2.2.1.3 NaBH4 as the Reducing Agent 26

2.2.1.4 Other Reducing Agents 27

VI Contents

2.2.2 Characterization of IL-Supported or Mediated MNPs 282.2.2.1 XPS and NMR 282.2.2.2 SEM and TEM 292.2.2.3 Molecular Dynamics Simulations 302.2.3 Hydrogenation Reactions 312.2.4 IL-Supported Pd NPs 322.2.5 IL-Supported Pt and Ir NPs 362.2.6 IL-Supported Ru NPs 372.2.6.1 IL-Supported Rh NPs 402.2.7 C–C Coupling Reactions 422.2.7.1 Suzuki Reaction 422.2.7.2 Mizoroki–Heck Reaction 452.2.7.3 Stille Reaction 472.2.7.4 Sonogashira Reaction 482.2.7.5 Ullmann Reaction 482.2.8 Brief Summary 492.3 Reactions Catalyzed by Solid-Supported IL: Heterogeneous Catalysis

with Homogeneous Performance 502.3.1 Introduction 502.3.1.1 Design, Preparation, and Properties of Supported IL-Phase

Catalysis 512.3.2 Design, Preparation, and Properties of Silica Gel-Confined IL

Catalysts 552.3.2.1 Design, Preparation, and Properties of Covalently Supported IL

Catalysts 562.3.3 Catalytic Reaction with Supported IL Catalysts 572.3.3.1 Catalytic Hydrogenation 572.3.3.2 Selective Oxidation 612.3.3.3 Catalytic Carbonylation Reaction 632.3.3.4 Water-Gas Shift Reaction 702.3.3.5 Isomerization and Oligomerization 722.3.3.6 Alkylation and Esterification Reactions 732.3.3.7 Asymmetric Catalysis 742.3.3.8 Enzyme Catalysis 772.3.4 Brief Summary 792.4 Outlook 80

References 80

3 Heterogeneous Catalysis with Organic–Inorganic Hybrid Materials 85Sang-Eon Park and Eun-Young Jeong

3.1 Introduction 853.1.1 Ordered Mesoporous Silica 853.1.2 Organic–Inorganic Hybrid Materials 883.1.3 Heterogeneous Catalysis 893.2 Organic–Inorganic Hybrid Materials 91

Contents VII

3.2.1 General Advantages of Organic–Inorganic Hybrid Materials 913.2.2 Grafting and Co-Condensation 913.2.2.1 Amine Groups 913.2.2.2 Ionic Liquids (ILs) 933.2.2.3 Others 953.2.3 Periodic Mesoporous Organosilicas (PMOs) 963.2.3.1 Synthesis of PMOs with Surfactants 963.2.3.2 Aliphatic PMO 973.2.3.3 Aromatic PMO 983.2.3.4 Hybrid Periodic Mesoporous Organosilica (HPMO) 983.3 Catalysis of Organic–Inorganic Hybrid Materials 993.3.1 Catalytic Application of Organic-Functionalized Mesoporous Silica by

Grafting and Co-Condensation Method 993.3.1.1 Knoevenagel Condensation 993.3.1.2 Aldol Condensation 993.3.1.3 Esterification of Alcohol 1033.3.2 Catalytic Application of Periodic Mesoporous Organosilica 1043.3.3 Chiral Catalysis 1053.3.4 Photocatalysis 1063.4 Summary and Conclusion 107

References 108

4 Homogeneous Asymmetric Catalysis Using Immobilized ChiralCatalysts 111Lei Wu, Ji Liu, Baode Ma, and Qing-Hua Fan

4.1 Introduction 1114.2 Soluble Polymeric Supports and Catalyst Separation Methods 1124.2.1 Types of Soluble Polymeric Supports 1124.2.2 Immobilized Catalyst Separation Methods 1144.3 Chiral Linear Polymeric Catalysts 1144.4 Chiral Dendritic Catalysts 1264.5 Helical Polymeric Catalysts 1394.6 Conclusion and Prospects 143

Acknowledgments 146References 146

5 Endeavors to Bridge the Gap between Homo- and HeterogeneousAsymmetric Catalysis with Organometallics 149Xingwang Wang, Zheng Wang, and Kuiling Ding

5.1 General Introduction 1495.2 Combinatorial Approach for Homogeneous Asymmetric

Catalysis 1515.2.1 The Principle of Combinatorial Approach to Chiral Catalyst

Discovery 1525.2.2 Ti(IV)-Catalyzed Enantioselective Reactions 153

VIII Contents

5.2.2.1 Schiff Base/Ti(IV)-Catalyzed Asymmetric Hetero-Diels–AlderReaction 153

5.2.2.2 BINOLate/Ti(IV)-Catalyzed Asymmetric Hetero-Diels–AlderReaction 154

5.2.2.3 BINOLate/Ti-Catalyzed Asymmetric Carbonyl–EneReaction 156

5.2.2.4 BINOLate/Ti-Catalyzed Asymmetric Ring-Opening Aminolysis ofEpoxides 158

5.2.3 Zn Complex-Catalyzed Enantioselective Reactions 1595.2.3.1 Chiral Amino Alcohol/Zn/Racemic Amino Alcohol-Catalyzed

Asymmetric Diethylzinc Addition to Aldehydes 1595.2.3.2 BINOLate/Zn/Diimine-Catalyzed Asymmetric Diethylzinc Addition

to Aldehydes 1625.2.3.3 BINOLate/Zn/Diimine-Catalyzed Asymmetric Hetero-Diels–Alder

Reaction 1655.2.4 Ru Complex-Catalyzed Enantioselective Reactions 1685.2.4.1 Achiral Monophosphine/Ru/Chiral Diamine-Catalyzed Asymmetric

Hydrogenation of Ketones 1685.2.4.2 Achiral Bisphosphine/Ru/Chiral Diamine-Catalyzed Asymmetric

Hydrogenation of Ketones 1715.3 Self-Supporting Approach for Heterogeneous Asymmetric

Catalysis 1725.3.1 The Principle of Design and Generation of Self-Supported

Catalysts 1755.3.2 Self-Supported BINOLate/Ti(IV)-Catalyzed Asymmetric

Carbonyl–Ene Reaction 1785.3.3 Self-Supported BINOLate/Ti(IV)-Catalyzed Asymmetric Sulfoxidation

Reaction 1785.3.4 Self-Supported BINOLate/La(III)-Catalyzed Asymmetric

Epoxidation 1805.3.5 Self-Supported BINOLate/Zn(II)-Catalyzed Asymmetric

Epoxidation 1835.3.6 Self-Supported Noyori-Type Ru(II)-Catalyzed Asymmetric

Hydrogenation 1855.3.7 Self-Supported MonoPhos/Rh(I)-Catalyzed Asymmetric

HydrogenationReactions 187

5.3.7.1 Covalent Bonded Bridging Ligands for Self-Supported Catalysts 1875.3.7.2 Hydrogen-Bonded Bridging Ligands for Self-Supported

Catalysts 1905.3.7.3 Metal-Coordinated Bridging Ligands for Self-Supported

Catalysts 1925.4 Conclusions and Outlook 194

Acknowledgments 195References 195

Contents IX

6 Catalysis in and on Water 201Shifang Liu and Jianliang Xiao

6.1 Introduction 201

6.2 Catalytic Reactions in and ‘‘on’’ Water 202

6.2.1 Hydroformylation 202

6.2.2 Hydrogenation 208

6.2.2.1 Achiral Hydrogenation 209

6.2.2.2 Asymmetric Hydrogenation 215

6.2.3 C–C Bond Formation 220

6.2.3.1 Diels–Alder Reaction 220

6.2.3.2 Friedel–Crafts Reaction 224

6.2.3.3 Suzuki–Miyaura Coupling 226

6.2.3.4 Heck Reaction 234

6.2.3.5 Alcohol Oxidation 238

6.3 Conclusions 244

References 244

7 A Green Chemistry Strategy: Fluorous Catalysis 253Zhong-Xing Jiang, Xuefei Li, and Feng-Ling Qing

7.1 History of Fluorous Chemistry 253

7.2 Basics of Fluorous Chemistry 254

7.3 Fluorous Metallic Catalysis 263

7.3.1 Fluorous Palladacycle Catalysts 264

7.3.2 Fluorous Pincer Ligand-Based Catalysts 265

7.3.3 Fluorous Immobilized Nanoparticles Catalysts 267

7.3.4 Fluorous Palladium-NHC Complexes 270

7.3.5 Fluorous Phosphine-Based Palladium Catalyst 271

7.3.6 Fluorous Grubbs’ Catalysts 272

7.3.7 Fluorous Silver Catalyst 273

7.3.8 Fluorous Wilkinson Catalyst 273

7.3.9 Miscellaneous Fluorous Catalysts 274

7.4 Fluorous Organocatalysis 275

7.4.1 Asymmetric Aldol Reaction 276

7.4.2 Morita–Baylis–Hillman Reaction 277

7.4.3 Asymmetric Michael Addition Reaction 278

7.4.4 Catalytic Oxidation Reaction 278

7.4.5 Catalytic Acetalization Reaction 279

7.4.6 Catalytic Condensation Reaction 279

7.4.7 Catalytic Asymmetric Fluorination Reaction 280

7.5 Conclusion 281

References 281

X Contents

8 Emulsion Catalysis: Interface between Homogeneous andHeterogeneous Catalysis 283Yan Liu, Zongxuan Jiang, and Can Li

8.1 Introduction 2838.1.1 Water in Chemistry 2838.1.2 Water as Solvent 2838.1.3 Emulsion 2858.1.4 Emulsion Catalysis 2858.2 Emulsion Catalysis in the Oxidative Desulfurization 2878.2.1 Emulsion Catalytic Oxidative Desulfurization Using H2O2 as

Oxidant 2878.2.2 Emulsion Catalytic Oxidative Desulfurization Using O2 as

Oxidant 2968.3 Emulsion Catalysis in Lewis Acid-Catalyzed Organic Reactions 2978.4 Emulsion Catalysis in Reactions with Organocatalysts 3038.4.1 Aldol Reaction 3038.4.2 Michael Addition 3098.5 Emulsion Formed with Polymer-Bounded Catalysts 3128.5.1 Emulsion Catalysis Participated by Metal Nanoparticles Stabilized

by Polymer 3128.5.2 Polymer-Bounded Organometallic Catalysts in Emulsion

Catalysis 3158.6 Conclusion and Perspective 319

References 320

9 Identification of Binding and Reactive Sites in Metal Cluster Catalysts:Homogeneous–Heterogeneous Bridges 325Michael M. Nigra and Alexander Katz

9.1 Introduction 3259.2 Control of Binding in Metal-Carbonyl Clusters via Ligand Effects 3329.3 Imaging of CO Binding on Noble Metal Clusters 3379.4 Imaging of Open Sites in Metal Cluster Catalysis 3399.5 Elucidating Kinetic Contributions of Open Sites: Kinetic Poisoning

Experiments Using Organic Ligands 3409.6 More Approaches to Poisoning Open Catalytic Active Sites to Obtain

Structure Function Relationships 3439.6.1 Using Atomic Layer Deposition of Al2O3 to Block Sites on Pd/Al2O3

Catalysts 3439.6.2 Bromide Poisoning of Active Sites on Au/TiO2 Catalysts for CO

Oxidation Reactions 3449.6.3 Bromide Poisoning of Active Sites on Au/TiO2 Catalysts for

Water-Gas Shift Reactions 3459.7 Supported Molecular Iridium Clusters for Ethylene

Hydrogenation 346

Contents XI

9.8 Summary and Outlook 348References 349

10 Catalysis in Porous-Material-Based Nanoreactors: a Bridge betweenHomogeneous and Heterogeneous Catalysis 351Qihua Yang and Can Li

10.1 Introduction 35110.2 Preparation of Nanoreactors Based on Porous Materials 35210.2.1 Mesoporous Silicas 35310.2.2 Metal-Organic Frameworks (MOFs) 35410.2.3 Surface Modification of Nanoreactors 35510.2.3.1 Surface Modification of Mesoporous Silicas (MSs) 35510.2.3.2 Surface Modification of MOFs 35810.3 Assembly of the Molecular Catalysts in Nanoreactors 35910.3.1 Incorporating Chiral Molecular Catalysts in Nanoreactors through

Covalent-Bonding Methods 35910.3.2 Immobilizing Chiral Molecular Catalysts in Nanoreactors through

Noncovalent Bonding Methods 36310.3.2.1 Introduction of Molecular Catalysts into Nanoreactors through

Noncovalent Bonding Methods 36310.3.2.2 Encapsulating Molecular Catalyst in Nanoreactors by Reducing the

Pore Entrance Size 36610.4 Catalytic Reactions in Nanoreactors 36910.4.1 Pore Confinement Effect 36910.4.2 Enhanced Cooperative Activation Effect in Nanoreactors 37710.4.2.1 The Kinetic Resolution of Epoxides 37710.4.2.2 Water Oxidation Reactions 38010.4.2.3 Epoxide Hydration 38110.4.3 Isolation Effect in Nanoreactors 38210.4.3.1 Selectivity Control 38210.4.3.2 Inhibiting Dimerization of Molecular Catalysts 38510.4.4 Microenvironment Engineering of Nanoreactors 38510.4.5 Influence of the Porous Structure on the Catalytic Performance of

Nanoreactors 38810.4.6 Catalytic Nanoreactor Engineering 39010.5 Conclusions and Perspectives 390

References 392

11 Heterogeneous Catalysis by Gold Clusters 397Jiahui Huang and Masatake Haruta

11.1 Introduction 39711.2 Preparation of Gold Clusters 39911.2.1 Chemical Reduction 39911.2.1.1 Phosphorus Ligands 40111.2.1.2 Sulfur Ligands 401

XII Contents

11.2.1.3 Amide Ligands 40211.2.2 Physical Vapor Deposition 40311.2.3 Electrical Reduction 40411.2.4 Other Methods 40411.3 Characterization of Gold Clusters 40511.4 Catalysis by Gold Clusters 40711.4.1 Selective Hydrogenation 40711.4.2 Selective Oxidation 40911.4.2.1 Oxygen Activation 40911.4.2.2 Alkanes 41011.4.2.3 Alkenes 41111.4.2.4 Alcohols 41411.4.3 CO Oxidation 41511.4.4 Organic Synthesis 41911.5 Conclusions and Perspectives 420

References 421

12 Asymmetric Phase-Transfer Catalysis in Organic Synthesis 425Shen Li and Jun-An Ma

12.1 Introduction 42512.2 Chiral Phase-Transfer Catalysts 42612.2.1 Chiral Crown Ethers – Cation-Binding Phase-Transfer

Catalysts 42612.2.2 Chiral Cation Phase-Transfer Catalysts 42812.2.2.1 Chiral Quaternary Ammonium Salts 42812.2.2.2 Chiral Quaternary Phosphonium Salts 44012.2.3 Chiral Anion Phase-Transfer Catalysts 44112.3 Asymmetric Phase-Transfer Catalytic Reactions and

Applications 44312.3.1 Asymmetric Phase-Transfer Reactions of Glycine Imine

Derivatives 44312.3.1.1 Asymmetric Alkylations 44312.3.1.2 Asymmetric Conjugate Additions 44712.3.1.3 Asymmetric Aldol and Mannich Condensations 44812.3.2 Asymmetric Phase-Transfer Reactions of 1,3-Dicarbonyl

Derivatives 45012.3.3 Asymmetric Phase-Transfer Reactions of Oxindoles 45412.3.4 Asymmetric Phase-Transfer Reactions of Nitroalkanes 45512.3.5 Asymmetric Phase-Transfer Cyclization Reactions 45712.3.6 Asymmetric Phase-Transfer Fluorination and Trifluoromethylation

Reactions 45812.3.7 Asymmetric Phase-Transfer Cyanation Reactions 45912.3.8 Other Asymmetric Phase-Transfer Reactions 46012.4 Concluding Remarks 461

References 461

Contents XIII

13 Catalysis in Supercritical Fluids 469Zhaofu Zhang, Jun Ma, and Buxing Han

13.1 Introduction 46913.2 Features of Supercritical Fluids and Related Catalytic Reactions 47013.2.1 Properties of Supercritical Fluids 47013.2.2 Features of Reactions in Supercritical Fluids 47113.3 Examples of the Reactions in SCFs 47213.3.1 Hydrogenation of Organic Substances 47213.3.2 Hydrogenation of CO2 47613.3.3 Hydroformylation Reactions 47813.3.4 Oxidations 47913.3.5 Alkylation 48113.3.6 CO2 Cycloaddition to Epoxide 48213.4 Summary and Conclusions 483

References 484

14 Hydroformylation of Olefins in Aqueous–Organic Biphasic CatalyticSystems 489Hua Chen, Xueli Zheng, and Xianjun Li

14.1 Introduction 48914.2 Water-Soluble Rhodium–Phosphine Complex Catalytic Systems 49014.3 Mechanism 49114.4 Hydroformylation of Lower Olefins 49314.4.1 Ethylene 49314.4.2 Propene 49414.4.3 Butene 49614.5 Hydroformylation of Higher Olefins 49714.5.1 Supported Aqueous-Phase Catalysts 49814.5.2 Cosolvent 49914.5.3 Surfactants 50014.5.4 Cyclodextrins 50314.5.5 Thermoregulated Inverse Phase-Transfer Catalysts 50514.6 Hydroformylation of Internal Olefins 50614.7 Conclusion and Outlook 508

References 508

15 Recent Progress in Enzyme Catalysis in Reverse Micelles 511Xirong Huang and Luyan Xue

15.1 Introduction 51115.2 Enzyme Catalysis in Molecular Organic Solvent-Based Reverse

Micelles 51315.2.1 Effect of Interfacial Property of Reverse Micelles on Enzyme

Catalysis 51315.2.1.1 Effect of the Electrical Property of the Interface 51315.2.1.2 Effect of the Size and Structure of Surfactant Head Group 516

XIV Contents

15.2.2 Effect of Additives on Enzyme Catalysis in Reverse Micelles 52115.2.2.1 Ionic Liquids as Additives 52115.2.2.2 Nanomaterials as Additives 52515.2.3 Relationship between the Conformation and the Activity of Enzymes

in Reverse Micelles 52815.2.4 Pseudophase Model and Enzyme-Catalyzed Reaction Kinetics in

Reverse Micelles 53015.3 Enzyme Catalysis in Ionic Liquid−Based Reverse Micelles 53115.3.1 Microemulsification of Hydrophobic Ionic Liquids 53115.3.2 Ionic Liquids as Surfactants 53715.4 Application of Enzyme Catalysis in Reverse Micelles 53715.4.1 Application in Biotransformation 53815.4.2 Reverse Micelle-Based Gel and Its Application for Enzyme

Immobilization 54115.5 Concluding Remarks 543

References 544

16 The Molecular Kinetics of the Fischer–Tropsch Reaction 553Rutger A. van Santen, Minhaj M. Ghouri, Albert J. Markvoort, and EmielJ. M. Hensen

16.1 Introduction 55316.2 Basics of the Fischer–Tropsch Kinetics 55616.2.1 Mechanistic Background of the Carbide-Based Mechanism 55616.2.1.1 Initiation 55716.2.1.2 Propagation 55816.2.1.3 Termination 55916.2.2 General Kinetics Considerations 55916.2.2.1 Some Mathematical Expressions 55916.3 Molecular Microkinetics Simulations 56416.3.1 Analysis of Microkinetics Results 57616.3.1.1 Monomer Formation Limited Kinetics Limit versus Chain Growth

Model 57616.3.1.2 Methane Formation versus Fischer–Tropsch Kinetics 58316.4 The Lumped Kinetics Model 58616.4.1 The Single Reaction Center Site Model 58616.4.2 The Dual Reaction Center Site Model 59216.5 Transient Kinetics 59416.6 Conclusion and Summary 599

References 604

Index 607

XV

Preface

Homogeneous catalysis and heterogeneous catalysis represent the subdisciplines oftraditional catalysis. Homogeneous catalysis is a sequence of reactions that involvesa catalyst in the same phase as the reactants, and generally uses organic molecules,organometallic complexes, acid/base, or salt as catalysts. Usually, homogeneouscatalytic reactions have well-defined active sites that provide relatively high activityand selectivity. However, most homogeneous catalytic processes meet the difficultyin large-scale applications including recycling of the catalyst, stability, and handlingin industrial processes. Heterogeneous catalysts are not in the same phase as thereactants. Typically, heterogeneous catalysis involves the use of solid catalysts inliquid or gas phases. Therefore, heterogeneous catalysis offers the advantage thatproducts are readily separated from the catalyst and heterogeneous catalysts areoften more stable than homogeneous catalysts. Heterogeneous catalysis alwaysinvolves the mass transfer and diffusion process among the reactants, productsand solid catalysts. Moreover, heterogeneous catalysts are more complex and theiractive sites and relevant mechanisms are not well understood for most cases.

For a long time, unfortunately, homogeneous catalysis and heterogeneouscatalysis have been developing independently, possibly because the scientistsof these fields have been working in separated disciplines: homogeneous catalysisresearchers mostly belong to organic chemistry, while heterogeneous catalysisresearchers major in chemical engineering or physical chemistry. However, thescientific basis for the homogeneous and heterogeneous catalysis is commonessentially. Although heterogeneous catalysis involves many complex processesfrom macro to micro and down to nano-scale, the active sites distribute at theatomic or molecular scale and catalytic elementary reactions take place on theactive sites of single atom or atomic cluster in nano space, which is similar to themolecular catalysis in homogeneous state.

In fact, much effort has been devoted to bridging the homogeneous catalysis andheterogeneous catalysis. The progress includes the development of heterogeneouscatalysis by means of strategies on the immobilization of molecular catalysts onsolid supports for the purpose of taking the advantage of both homogeneouscatalysis and heterogeneous catalysis. However, there are always some obstaclesfor achieving perfect performance. Using this strategy, the immobilized molecularcatalysts usually exhibit lower performance than their homogeneous counterparts.Moreover, catalyst leaching may occasionally cause problems for an immobilized

XVI Preface

catalyst because of the unstable linkage between the catalyst and the support. Fromour personal view point, understanding the relationship between the homogeneousand heterogeneous catalysis on the molecular level is the prerequisite for designingand preparing advanced catalysts with the merits of both homogeneous andheterogeneous catalysis. However, this was not well organized before. Moreover,to clarify these relationships is also important to bridge the enzyme catalysis andtraditional chemical catalysis, as the activation model of enzyme catalysis actuallyfalls in between the homogeneous catalysis and heterogeneous catalysis.

This book, which comprises 16 chapters, is intended to give an extensivedescription of the research progress on the catalysis between homogeneous andheterogeneous catalysis. The entire content of the book is divided into threesections according to the states of reactants and catalysts: solid–liquid, solid–gasand liquid–liquid system.

Solid–liquid catalytic system included in Chapters 1, 3, 4, 5, and 10 mainlydeals with that molecular catalysts immobilized on the solid materials via chemicalbonding or physical adsorption. Chapter 1 provides an over-review to acid–basecooperative catalysis by organofunctionalized solid surfaces. Chapter 3 summa-rizes the background and recent development of various types of functionalorganic–inorganic hybridized mesoporous materials in the catalytic applications.Chapter 4 presents the detail of the immobilization of a chiral catalyst on solublepolymers, that is, linear polymers, dendrimers and helical polymer and its applica-tion on the different asymmetric reactions. Chapter 5 describes that highly efficienthomo- and heterogeneous chiral organometallic catalysts were developed throughcombinatorial and self-supporting strategy. Chapter 10 reviews the recent researchadvances in catalytic reactions in porous-material-based nanoreactors exhibitingadvantages from both homogeneous and heterogeneous catalysis, including thepreparation methods for nanoreactor, the surface modification of nanoreactors,and various strategies for the encapsulation of the molecular catalysts in nanoreac-tors. Furthermore, some important issues concerning the porous-material-basednanoreactor, such as the pore confinement effect, the isolation effect, and thecooperative activation effect are also discussed in this chapter.

The catalysis in liquid–liquid biphasic system is addressed in Chapters 2, 6, 7,8, 12, 13, 14 and 15. Thus, supported ion-liquid catalyst system is discussed inChapter 2. The potential and limitations of supercritical fluids as media for catalyticreactions are discussed in Chapter 13. While water-based reactions are describedin Chapters 6, 8, 12 and 14 according to the different strategies and reactions.Chapter 2 shows that some of the metal-catalyzed reactions can be carried out inor on water. In Chapter 8, emulsion catalysis has been demonstrated to be quitea useful strategy in the aqueous–oil biphasic reaction. Phase transfer reagents arelike bridges for transferring the ionic salt reactants from aqueous phase into theorganic phase, which overcome the solubility problems of two phases. Chapter 12provides a general overview of this continuously growing field, focusing not onlyon the design of various types of chiral phase-transfer catalysts but also on theirrepresentative applications. Chapter 14 reviews the aqueous–organic biphasiccatalytic processes of olefin hydroformylation. Biocatalysis attracts more and more

Preface XVII

attention in the synthesis of chiral compounds and other fine chemicals, andnow it becomes a research hotspot. Reverse micelles, which are homogeneousmacroscopically but heterogeneous microscopically, are proved to be a promisingmedia in enzyme catalysis in Chapter 15.

Gas–solid catalytic reaction is the most common chemical process in theindustry. However, owing to the limitation of this book, only three chapters weredevoted to this theme. Chapter 11 describes the preparation of gold clusters and itsapplication on the solid–gas biphasic catalytic reaction. The clarification of catalyticmechanism and reactive sites is very important for designing more efficientcatalysts. So the identification of binding and reactive sites in metal cluster catalysisthrough imaging technique, kinetic study, and other methods are introduced inChapter 9. To reflect the importance of theoretical calculation on catalysis, themolecular kinetics of the Fischer–Tropsch reaction by computational chemistry isintroduced in Chapter 16.

We organized this book with the intention of not only bridging homogeneousand heterogeneous catalysis, but also for providing a platform for scientists fromdifferent disciplines to generate new ideas and thoughts by inspiring each other.

We sincerely thank all the authors for their excellent contributions, without whoseefforts this book would not have been possible. We also enjoyed the collaborationwith Wiley–VCH and would like to acknowledge Laserwords for their carefulediting work.

Dalian Can LiJanuary, 2014 Yan Liu

XIX

List of Contributors

Toshihide BabaTokyo Institute of TechnologyDepartment of EnvironmentalChemistry and Engineering4259 Nagatsuta-choMidori-kuYokohama 226-8502Japan

Hua ChenSichuan UniversityCollege of ChemistryNo. 24 South Section 1Yihuan RoadChengdu 610064P.R. China

Youquan DengLanzhou Institute of ChemicalPhysicsChinese Academy of SciencesCentre for Green Chemistry andCatalysisTianshui Middle RoadLanzhou 730000P.R. China

Kuiling DingShanghai Institute of OrganicChemistryChinese Academy of SciencesState Key Laboratory ofOrganometallic Chemistry345 Lingling RoadShanghai 200032P.R. China

Qing-Hua FanInstitute of ChemistryChinese Academy of Sciences(CAS)Beijing National Laboratory forMolecular ScienceCAS Key Laboratory of MolecularRecognition and Function2 Zhongguancun North FirstStreetBeijing 100190P.R. China

XX List of Contributors

Minhaj M. GhouriEindhoven University ofTechnologyInstitute for Complex MolecularSystemsDen Dolech 2, PO Box 5135600 MBEindhovenThe Netherlands

and

Eindhoven University ofTechnologyLaboratory of Inorganic MaterialsChemistryDepartment of ChemicalEngineering and ChemistryBuilding HelixDen Dolech 2, PO Box 5135600 MBEindhovenThe Netherlands

Buxing HanChinese Academy of SciencesBeijing National Laboratory forMolecular ScienceCAS Key Laboratory of ColloidInterface and ChemicalThermodynamicsInstitute of ChemistryZhongguancun North First StreetBeijing 100190P.R. China

Masatake HarutaChinese Academy of SciencesState Key Laboratory of CatalysisDalian Institute of ChemicalPhysics457 Zhongshan RoadDalian 116023P.R. China

and

Chinese Academy of SciencesGold Catalysis Research CenterDalian Institute of ChemicalPhysics457 Zhongshan RoadDalian 116023P.R. China

and

Tokyo Metropolitan UniversityDepartment of Applied ChemistryFaculty of Urban EnvironmentalSciences1-1 Minami-OsawaHachiojiTokyo 192-0397Japan

Emiel J. M. HensenEindhoven University ofTechnologyLaboratory of Inorganic MaterialsChemistryDepartment of ChemicalEngineering and ChemistryBuilding HelixDen Dolech 2, PO Box 5135600 MBEindhovenThe Netherlands

List of Contributors XXI

Jiahui HuangChinese Academy of SciencesState Key Laboratory of CatalysisDalian Institute of ChemicalPhysics457 Zhongshan RoadDalian 116023P.R. China

and

Chinese Academy of SciencesGold Catalysis Research CenterDalian Institute of ChemicalPhysics457 Zhongshan RoadDalian 116023P.R. China

Xirong HuangShandong UniversityKey Laboratory of Colloid &Interface Chemistry of theEducation Ministry of ChinaNo 27 Shanda NanluJinan 250100P.R. China

Yasuhiro IwasawaThe University ofElectro-CommunicationsInnovation Research Center forFuel Cells1-5-1 ChofugaokaChofuTokyo 182-8585Japan

Eun-Young JeongInha UniversityDepartment of ChemistryLaboratory of Nano-GreenCatalysis and Nano Center forFine Chemicals FusionTechnology253 YonghyundongNamguIncheon 402-751South Korea

Zhong-Xing JiangSchool of PharmaceuticalSciencesWuhan University185 Donghu RoadWuhan 430071P.R. China

Zongxuan JiangChinese Academy of SciencesState Key Laboratory of CatalysisDalian Institute of ChemicalPhysics457, Zhongshan RoadDalian 116023P.R. China

Alexander KatzUniversity of CaliforniaDepartment of Chemical andBiomolecular EngineeringMC 1462BerkeleyCA 94720USA

XXII List of Contributors

Can LiChinese Academy of SciencesState Key Laboratory of CatalysisDalian Institute of ChemicalPhysics457, Zhongshan RoadDalian 116023P.R. China

Shen LiTianjin UniversityDepartment of Chemistry92 Weijin RoadTianjin 300072P.R. China

Xianjun LiSichuan UniversityCollege of ChemistryNo. 24 South Section 1Yihuan RoadChengdu 610064P.R. China

Xuefei LiSchool of PharmaceuticalSciencesWuhan University185 Donghu RoadWuhan 430071P.R. China

Ji LiuInstitute of ChemistryChinese Academy of Sciences(CAS)Beijing National Laboratory forMolecular ScienceCAS Key Laboratory of MolecularRecognition and Function2 Zhongguancun North FirstStreetBeijing 100190P. R. China

Shifang LiuUniversity of Oxford BegbrokeScience ParkCCM ResearchCentre for Innovation andEnterpriseYartonOX5 1PFUK

and

Chongqing University of Arts andSciencesResearch Centre for MaterialsInterdisciplinary ScienceChongqing 402160P.R. China

Yan LiuChinese Academy of SciencesState Key Laboratory of CatalysisDalian Institute of ChemicalPhysics457, Zhongshan RoadDalian 116023P.R. China

List of Contributors XXIII

Baode MaInstitute of ChemistryChinese Academy of Sciences(CAS)Beijing National Laboratory forMolecular ScienceCAS Key Laboratory of MolecularRecognition and Function2 Zhongguancun North FirstStreetBeijing 100190P. R. China

Jun-An MaTianjin UniversityDepartment of Chemistry92 Weijin RoadTianjin 300072P.R. China

Jun MaChinese Academy of SciencesBeijing National Laboratory forMolecular ScienceCAS Key Laboratory of ColloidInterface and ChemicalThermodynamicsInstitute of ChemistryZhongguancun North First StreetBeijing 100190P.R. China

Albert J. MarkvoortEindhoven University ofTechnologyInstitute for Complex MolecularSystemsDen Dolech 2, PO Box 5135600 MBEindhovenThe Netherlands

and

Eindhoven University ofTechnologyComputational Biology GroupDepartment of BiomedicalEngineeringDen Dolech 2, PO Box 5135600 MBEindhovenThe Netherlands

Ken MotokuraTokyo Institute of TechnologyDepartment of EnvironmentalChemistry and Engineering4259 Nagatsuta-choMidori-kuYokohama 226-8502Japan

Michael M. NigraUniversity of CaliforniaDepartment of Chemical andBiomolecular EngineeringMC 1462BerkeleyCA 94720USA

Sang-Eon ParkInha UniversityDepartment of ChemistryLaboratory of Nano-GreenCatalysis and Nano Center forFine Chemicals FusionTechnology253 YonghyundongNamguIncheon 402-751South Korea

XXIV List of Contributors

Feng-Ling QingShanghai Institute of OrganicChemistryChinese Academy of SciencesKey Laboratory of OrganofluorineChemistry345 Lingling RoadShanghai 200032P.R. China

Rutger A. van SantenEindhoven University ofTechnologyInstitute for Complex MolecularSystemsDen Dolech 2, PO Box 5135600 MBEindhovenThe Netherlands

and

Eindhoven University ofTechnologyLaboratory of Inorganic MaterialsChemistryDepartment of ChemicalEngineering and ChemistryBuilding HelixDen Dolech 2, PO Box 5135600 MBEindhovenThe Netherlands

Feng ShiLanzhou Institute of ChemicalPhysicsChinese Academy of SciencesCentre for Green Chemistry andCatalysisTianshui Middle RoadLanzhou 730000P.R. China

Xingwang WangSoochow UniversityCollege of ChemistryChemical Engineering andMaterials ScienceSuzhou Industrial Park199 Rein-Ai RoadSuzhou 215123P.R. China

Zheng WangShanghai Institute of OrganicChemistryChinese Academy of SciencesState Key Laboratory ofOrganometallic Chemistry345 Lingling RoadShanghai 200032P.R. China

Lei WuNanjing Agricultural UniversityDepartment of ChemistryCollege of Sciences1 Weigang, Xuanwu DistrictNanjing 210095P. R. China

List of Contributors XXV

Jianliang XiaoUniversity of LiverpoolDepartment of ChemistryOxford StreetLiverpool L69 7ZDUK

Luyan XueShandong UniversityKey Laboratory of Colloid &Interface Chemistry of theEducation Ministry of ChinaNo 27 Shanda NanluJinan 250100P.R. China

Qihua YangChinese Academy of SciencesState Key Laboratory of CatalysisDalian Institute of ChemicalPhysics457, Zhongshan RoadDalian 116023P.R. China

Qinghua ZhangLanzhou Institute of ChemicalPhysicsChinese Academy of SciencesCentre for Green Chemistry andCatalysisTianshui Middle RoadLanzhou 730000China

Zhaofu ZhangChinese Academy of SciencesBeijing National Laboratory forMolecular ScienceCAS Key Laboratory of ColloidInterface and ChemicalThermodynamicsInstitute of ChemistryZhongguancun North First StreetBeijing 100190China

Xueli ZhengSichuan UniversityCollege of ChemistryNo. 24 South Section 1Yihuan RoadChengdu 610064P.R. China

1

1Acid–Base Cooperative Catalysis for Organic Reactions byDesigned Solid Surfaces with Organofunctional GroupsKen Motokura, Toshihide Baba, and Yasuhiro Iwasawa

1.1Introduction

This chapter deals with acid–base bifunctional heterogeneous catalyst surfaceswith organofunctional groups. One of the most important issues for bifunctionalheterogeneous catalysis is the coexistence of incompatible catalytic species, suchas acid and base, nearby on a same solid particle surface. In nucleophilic reactions,acid–base bifunctional catalysts enable the activation of both nucleophilic andelectrophilic substrates to enhance their reactions. Generally, there are two types ofcatalytic nucleophilic addition reactions: the first one is activation of the nucleophileprecursors by basic catalysts to abstract their acidic parts, such as α-hydrogen atoms,and the other is the lowering of lowest unoccupied molecular orbital (LUMO) levelsof electrophiles by interaction with Brønsted or Lewis acidic catalysts. From this fact,an ideal pathway for the nucleophilic reaction is dual activation of both electrophilesand nucleophiles by acidic and basic functions of catalysts, respectively (Scheme 1.1)[1]. Strongly acidic and basic species in a solution reactor induces neutralizationimmediately, thus affording inactive salts. However, immobilization of both theacidic and basic species on solid surfaces can avoid mutual neutralization. Somecatalytic reaction systems containing both acidic and basic solid catalysts as separatecatalyst particles have been reported for one-pot reaction sequences [2]. In thesereaction systems, the acid and base sites are immobilized on different catalystparticles. Therefore, it is difficult to accelerate a single reaction step by cooperativeactivation of two substrates by both acid and base sites.

Immobilization of acidic and basic species nearby on a same solid surface cancreate a bifunctional catalytic surface possessing acid and base species that areable to participate in a single reaction step, resulting in significant acceleration ofthe catalytic reaction. Several reviews have been published on such heterogeneousacid–base catalysts having organic functional groups [3]. These heterogeneousacid–base bifunctional catalysts can be categorized into the following two types:(i) catalysts possessing both immobilized acidic and basic organic groups on theirsurfaces and (ii) catalysts possessing immobilized basic organic groups and acidsites derived from their support surfaces. In this chapter, these two types of

Bridging Heterogeneous and Homogeneous Catalysis: Concepts, Strategies, and Applications, First Edition.Edited by Can Li and Yan Liu.c© 2014 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2014 by Wiley-VCH Verlag GmbH & Co. KGaA.

2 1 Acid–Base Cooperative Catalysis for Organic Reactions

Acid Base

Solid surface

E Nu+ Product

E: electrophileN: nucleophile

E Nu

Scheme 1.1 Dual activation of both electrophile (E) and nucleophile (Nu) by acid andbase sites on a solid surface.

acid–base bifunctional catalysts are introduced and their catalytic performancesare discussed.

1.2Bifunctional Catalysts Possessing Both Acidic and Basic Organic Groups

1.2.1Urea–Amine Bifunctional Catalyst

In 2005, Lin and coworkers [4] demonstrated urea–amine bifunctionalized silicasurfaces for C–C couplings, such as aldol reaction of acetone, nitroaldol reaction(Henry reaction), and cyanosilylation. Surface structures of these immobilizedmesoporous silica nanospheres (MSNs) are shown in Figure 1.1. Both urea (UDP,ureidopropyl group) and amine (AEP, 3-(2-(2-aminoethylamino)ethylamino)propylgroup)-immobilized mesoporous silica nanosphere (AEP/UDP-MSN) showed thehighest catalytic activity among amine- or urea-immobilized MSNs (AEP- or UDP-MSN) (Scheme 1.2). In addition, these reactions were not significantly enhanced bya physical mixture of AEP-MSN and UDP-MSN. Scheme 1.3 represents a proposedreaction pathway of the aldol reaction involving activation of the aldehyde andacetone by urea (acid) and amine (base) group, respectively, on the silica surface.

(b)

N

NO

HH

H

Si

(a)

N H

Si

HN

NH2

(c)

N

NO

HH

H

Si

N H

Si

HN

NH2

Figure 1.1 Surface structures of (a) AEP-, (b) UDP-, and (c) AEP/UDP-immobilized meso-porous silica nanosphere (MSN).