A comprehensive resource on techniques and applications for immobilizing catalysts Catalyst Immobilization: Methods and Applications covers catalyst immobilization topics including technologies, materials, characterization, chemical activity, and recyclability. The book also presents innovative applications for supported catalysts, such as flow chemistry and machine-assisted organic synthesis. Written by an international panel of expert contributors, this book outlines the general principles of catalyst immobilization and explores different types of supports employed in catalyst heterogenization. The book?s chapters examine the immobilization of chiral organocatalysts, reactions in flow reactors, 3D printed devices for catalytic systems, and more. Catalyst Immobilization offers a modern vision and a broad and critical view of this exciting field. This important book: -Offers a guide to supported and therefore recyclable catalysts, which is one of the most important tools for developing a highly sustainable chemistry -Presents various immobilization techniques and applications -Explores new trends, such as 3D printed devices for catalytic systems -Contains information from a leading international team of authors Written for catalytic chemists, organic chemists, process engineers, biochemists, surface chemists, materials scientists, analytical chemists, Catalyst Immobilization: Methods and Applications presents the latest developments and includes a review of the innovative trends such as flow chemistry, reactions in microreactors, and beyond.
Preface xiii
1 Strategies to Immobilized Catalysts: A Key Tool for Modern Chemistry1Oriana Piermatti, Raed Abu-Reziq, and Luigi Vaccaro
1.1 Introduction 1
1.2 Catalysis 3
1.3 Heterogenization of Homogeneous Catalysts 3
1.3.1 Immobilization on Silica 4
1.3.1.1 Covalent Binding 6
1.3.1.2 Physical Entrapment 7
1.3.1.3 Electrostatic Interactions 7
1.3.1.4 Silica Microencapsulation 7
1.3.2 Polymeric Supports 9
1.3.2.1 Insoluble Polymers 10
1.3.2.2 Soluble Polymers 10
1.3.2.3 Polymeric Microcapsules 12
1.3.3 Other Supports 13
1.3.3.1 MetalOrganic Frameworks (MOFs) 13
1.3.3.2 Periodic Mesoporous Organosilicas (PMOs) 14
1.3.3.3 Magnetic Nanoparticles 14
1.3.3.4 Membranes 14
1.4 Characterization of Heterogeneous Catalysts 15
1.5 Conclusions 16
List of Abbreviations 16
References 17
2 Catalysts Immobilized onto Polymers23Shinichi Itsuno and Naoki Haraguchi
2.1 Introduction 23
2.2 Organocatalyst Immobilized onto Polymers 24
2.2.1 Polymer-Immobilized Cinchona Alkaloids 24
2.2.2 Polymer-Immobilized Proline Derivatives 30
2.2.3 Polymer-Immobilized Amino Acids 33
2.2.4 Polymer-Immobilized Pyrrolidine Derivatives 35
2.2.5 Polymer-Immobilized Chiral Amines 39
2.2.6 Polymer-Immobilized MacMillan Catalysts 42
2.2.7 Polymer-Immobilized Thioureas and Ureas 50
2.2.8 Polymer-Immobilized Chiral Phosphoric Acids 53
2.2.9 Polymer-Immobilized ChiralN-Heterocyclic Carbenes 55
2.3 Metal Catalysts Immobilized onto Polymers 56
2.3.1 Al: Polymer-Immobilized CatecholAl Catalyst 56
2.3.2 Au: Polymer-Immobilized TriazoleGold Catalyst 56
2.3.3 Co: Polymer-Immobilized Co(III)Salen Complex 57
2.3.4 Ir: Polymer-Immobilized Iridium Catalyst 58
2.3.5 Mo: Polymer-Immobilized Molybdenum Catalyst 60
2.3.6 Ni: Polymer-Immobilized Ni Catalyst 61
2.3.7 Pd: Polymer-Immobilized Pd Catalyst 62
2.3.8 Pt: Polymer-Immobilized Pt Nanoparticle 64
2.3.9 Rh: Polymer-Immobilized Rh Catalyst 65
2.3.10 Ru: Polymer-Immobilized Ru Catalyst 68
2.3.11 Ti: Polymer-Immobilized Ti Catalyst 69
2.3.12 Zn: Polymer-Immobilized Zn Catalyst 70
2.4 Outlook and Perspectives 71
2.5 List of Abbreviations 71
References 72
3 Modified Nanocarbons as Catalysts in Organic Processes77Vincenzo Campisciano, Michelangelo Gruttadauria, and Francesco Giacalone
3.1 Introduction 77
3.2 Fullerene-Based Catalysts 78
3.2.1 Organocatalysis 78
3.2.2 Organometallic Catalysis 82
3.3 Carbon Nanotubes-Based Catalysts 87
3.3.1 Supramolecular Functionalization 88
3.3.2 Covalent Functionalization 92
3.3.2.1 Organocatalysis 92
3.3.2.2 Organometallic Catalysis 93
3.4 Graphene-Based Catalysts 99
3.4.1 Supramolecular Functionalization 100
3.4.2 Covalent Functionalization 102
3.4.2.1 Organocatalysis 102
3.4.2.2 Organometallic Catalysis 105
3.5 Outlook and Perspectives: Conclusions 109
List of Abbreviations 110
References 111
4 Stereoselective Synthesis by Catalysts Supported on Magnetic Nanoferrite115Alessandro Ponti, Anna M. Ferretti, and GiorgioMolteni
4.1 Introduction 115
4.2 Structure and Properties of the Nanocatalysts 117
4.2.1 Structure Types 118
4.2.1.1 MNP and Catalyst 118
4.2.1.2 Structure Type I 119
4.2.1.3 Structure Type II 121
4.2.1.4 Other Structure Types 122
4.2.2 A Few Points About Synthesis 123
4.2.3 Magnetic Recovery 126
4.2.4 Recycling 128
4.3 Characterization of the Nanocatalysts 129
4.3.1 Morphology and Crystal Structure 130
4.3.2 Magnetic Properties 131
4.3.3 Identification of the Supported Species 132
4.3.4 Catalyst Loading and Leaching 135
4.3.5 DLS andZ-potential 136
4.4 Stereoselective Reactions 137
4.4.1 Substitutions 138
4.4.2 Condensations 139
4.4.3 Additions 141
4.4.4 Hydrogenations and Reductions 146
4.4.5 Epoxidations and Oxidations 148
4.4.6 CarbonCarbon Couplings 150
4.4.7 Kinetic Resolution of Racemic Mixtures 151
4.5 Conclusions 154
References 154
5 MetalOrganic Frameworks as Catalysts159Pillaiyar Puthiaraj and Wha-Seung Ahn
5.1 Introduction 159
5.2 Open Metal Sites as Reaction Sites 159
5.3 Organic Linkers in the Frameworks as Reaction Sites 162
5.3.1 Single-Linker MOFs 163
5.3.2 Mixed Linker MOFs 164
5.4 Multifunctional MOFs for Catalysis 166
5.5 Post-synthetic Grafting of Active Guest Species within MOFs 167
5.5.1 Grafting of Active Organic Species on Open Metal Sites 167
5.5.2 Grafting of Active Functional Groups on Organic Linkers 168
5.5.3 Grafting of Active Metal Complexes on Functionalized Organic Linkers 170
5.6 Encapsulation of Catalytically Active Guest Species Inside MOFs 173
5.6.1 Metal/Metal Oxide Nanoparticles on MOFs 173
5.6.2 Polyoxometalates (POMs) 175
5.6.3 Metalloporphyrins 176
5.7 MOF Membranes for Catalysis 177
5.8 Conclusions and Perspectives 182
Acknowledgments 182
References 183
6 Alternative Solvent Systems in Catalysis187Xavier Marset, Diego J. Ramón, and Gabriela Guillena
6.1 Introduction 187
6.2 Ionic Liquids as Solvents for Catalytic Organic Reactions 189
6.2.1 Transition-Metal Promoted Reaction in Ionic Liquids 189
6.2.2 Organocatalyzed Transformations Using Ionic Liquids 195
6.3 Deep Eutectic Solvents (DES) as Reaction Media in Catalysis 199
6.3.1 Non-innocent DES as Reaction Media 201
6.3.2 DES as Innocent Solvents for Recyclable Catalytic Transformations 205
6.3.2.1 Transition-Metal Catalyzed Processes 205
6.3.2.2 Organocatalyzed Reactions 207
6.4 Conclusion 211
List of Abbreviations 211
References 212
7 Immobilized Chiral Organocatalysts217Carles Rodríguez-Escrich
7.1 Introduction 217
7.2 Immobilized Chiral Aminocatalysts 219
7.2.1 Proline Derivatives 219
7.2.2 Diarylprolinol Derivatives 223
7.2.3 Imidazolidinones 227
7.2.4 Primary Amine Organocatalysts 230
7.2.5 Peptide Catalysts 233
7.3 Immobilized Chiral H-Bond Donors 235
7.3.1 Ureas and Thioureas 235
7.3.2 Squaramides 238
7.3.3 Amides and Sulfonamides 240
7.4 Immobilized Chiral Phosphoric Acids 241
7.5 Immobilized Lewis and Brønsted Base Organocatalysts 244
7.5.1 NHC Catalysts 245
7.5.2 Isothioureas 245
7.5.3 Amides as Lewis Bases 247
7.5.4 Brønsted Bases 247
7.6 Immobilized Phase Transfer Catalysts 249
7.7 Final Remarks and Future Perspectives 250
References 251
8 Catalyst Recycling in Continuous Flow Reactors257Alessandro Mandoli
8.1 Introduction 257
8.2 Types of Catalytic Flow Reactors and Parameters for Assessing Their Performance 259
8.3 Soluble Catalytic Systems 260
8.3.1 Metal Catalysts 263
8.3.1.1 Organic Solvent Nanofiltration 263
8.3.1.2 LiquidLiquid Biphasic Media and Supercritical Fluids 269
8.3.1.3 SLP Systems 273
8.3.1.4 Other Approaches 276
8.3.2 Metal-Free Catalysts 276
8.4 Insoluble Catalytic Systems 277
8.4.1 Packed-bed CFRs 281
8.4.2 Monolithic CFRs 282
8.4.3 Wall-coated CFRs 284
8.4.4 Metal Catalysts 285
8.4.4.1 Reduction Reactions 285
8.4.4.2 Cross-Coupling Reactions 289
8.4.5 Metal-Free Catalysts 290
8.5 Conclusions 293
List of Abbreviations 294
References 295
9 Membrane Reactors307Parisa Biniaz, Mohammad Amin Makarem, and Mohammad Reza Rahimpour
9.1 Introduction 307
9.2 Inert Membrane Reactor with Mobile Catalysts on the Reaction Side 308
9.2.1 Organic Solvent Nanofiltration 309
9.3 Catalytically Active Membrane Reactors 311
9.3.1 Hydrogenation Reactions 311
9.3.2 CarbonCarbon (CC) Cross-couplings 312
9.4 The Immobilized Catalyst in a Porous Membrane 313
9.5 Photocatalytic Organic Synthesis and Their Utilization in the Reduction of Organic Pollutant in Membrane Reactors 313
9.5.1 Photocatalytic Membrane Reactors 314
9.5.2 Membrane Reactors with Suspending Catalyst in the Reaction Mixture 314
9.6 The Applications of Membrane Reactors in the Biodiesel Transesterification 316
9.7 Conclusion and Future Trends 320
List of Abbreviations 320
References 321
10 Development of Polymer-Supported Transition-Metal Catalysts and Their Green Synthetic Applications325Takao Osako, Atsushi Ohtaka, and Yasuhiro Uozumi
10.1 Introduction 325
10.2 Polystyrene-Supported Transition-Metal Nanoparticle Catalysts 326
10.2.1 Background 326
10.2.2 CarbonCarbon Coupling Reactions in Water Catalyzed by Linear-Polystyrene-Stabilized Palladium(II) Oxide or Palladium Nanoparticles 327
10.2.2.1 Suzuki Coupling Reaction 327
10.2.2.2 Hiyama Coupling Reaction 330
10.2.2.3 Ullmann Coupling Reaction 333
10.2.2.4 Heck Reaction 334
10.2.2.5 Copper-Free Sonogashira Coupling Reaction 335
10.2.2.6 One-Pot Synthesis of Dibenzyls and 3-Arylpropanoic Acids 337
10.2.3 Linear-Polystyrene-Stabilized Platinum Nanoparticles: Preparation and Evaluation of Their Catalytic Activity in Water 338
10.2.3.1 Aerobic Oxidation of Alcohols 338
10.2.3.2 Hydrogen-Transfer Reduction in the Presence of Polystyrene-Stabilized Platinum Nanoparticles 340
10.3 Polystyrene-Poly(ethylene glycol)-Supported Transition-Metal Catalysts 341
10.3.1 Background 341
10.3.2 Aqueous Aerobic Flow Oxidation of Alcohols by Amphiphilic Resin-Dispersed Particles of Platinum (ARP-Pt) 342
10.3.3 Flow Hydrogenation of Olefins, Nitrobenzenes, and Aldehydes by Amphiphilic Resin-Dispersed Particles of Platinum (ARP-Pt) 349
10.3.4 Flow Hydrogenation by Amphiphilic Resin-Dispersed Particles of Iron (ARP-Fe) [110] 352
10.3.5 Aqueous Huisgen 1,3-Cycloaddition with an Amphiphilic Resin-Supported Triazine-Based Polyethyleneamine DendrimerCopper Catalyst 356
10.3.6 Aqueous Asymmetric 1,4-Addition with an Amphiphilic Resin-Supported Chiral DieneRhodium Complex 359
10.4 Conclusion 363
List of Abbreviations 363
References 364
11 3D Printed Devices for Catalytic Systems369Vittorio Saggiomo
11.1 Introduction 369
11.2 3D Printing 371
11.2.1 Fuse Deposition Modeling (FDM) 373
11.2.2 Millifluidic and Flow Reactors 374
11.2.3 Catalysts Embedded Thermoplastics 376
11.2.4 Resin Printers 382
11.2.5 Robocasting (Direct Ink Writing) 388
11.2.6 Powder Bed Fusion Printers 396
11.3 Conclusion 399
11.4 Outlook 402
List of Abbreviations 402
References 403
12 General Overview on Immobilization Techniques of Enzymes for Biocatalysis409María Romero-Fernández and Francesca Paradisi
12.1 Introduction 409
12.2 Physical Immobilization Methodologies 410
12.2.1 Entrapment 411
12.2.2 Encapsulation 411
12.3 Chemical Immobilization Methodologies 413
12.3.1 Non-covalent Bonding 413
12.3.1.1 Hydrophobic Adsorption 414
12.3.1.2 Ionic Exchange Adsorption 415
12.3.2 Covalent Bonding 418
12.4 Conclusion 426
List of Abbreviations 426
References 427
13 Immobilized Enzymes: Applications in Organic Synthesis437Hans-Jürgen Federsel, Jaan Pesti, and Matthew P. Thompson
13.1 Introduction: The Quest for Chemicals and the Role of Organic Synthesis 437
13.2 Enzymes as Enablers of Synthesis 441
13.3 Enzymes in Action: Immobilized Processes on Scale 444
13.4 Key Features of Systems Operating with Immobilized Enzymes 452
13.5 Future Perspectives: The Road Ahead 457
List of Abbreviations 459
References 460
Index 465
