Catalyst immobilization: methods and applications

Cover......Page 1
Title Page......Page 5
Copyright......Page 6
Contents......Page 7
Preface......Page 15
 1.1 Introduction......Page 17
 1.3 Heterogenization of Homogeneous Catalysts......Page 19
  1.3.1 Immobilization on Silica......Page 20
   1.3.1.1 Covalent Binding......Page 22
   1.3.1.4 Silica Microencapsulation......Page 23
  1.3.2 Polymeric Supports......Page 25
   1.3.2.2 Soluble Polymers......Page 26
   1.3.2.3 Polymeric Microcapsules......Page 28
   1.3.3.1 Metal–Organic Frameworks (MOFs)......Page 29
   1.3.3.4 Membranes......Page 30
 1.4 Characterization of Heterogeneous Catalysts......Page 31
 List of Abbreviations......Page 32
 References......Page 33
 2.1 Introduction......Page 39
  2.2.1 Polymer‐Immobilized Cinchona Alkaloids......Page 40
  2.2.2 Polymer‐Immobilized Proline Derivatives......Page 46
  2.2.3 Polymer‐Immobilized Amino Acids......Page 49
  2.2.4 Polymer‐Immobilized Pyrrolidine Derivatives......Page 51
  2.2.5 Polymer‐Immobilized Chiral Amines......Page 55
  2.2.6 Polymer‐Immobilized MacMillan Catalysts......Page 58
  2.2.7 Polymer‐Immobilized Thioureas and Ureas......Page 66
  2.2.8 Polymer‐Immobilized Chiral Phosphoric Acids......Page 69
  2.2.9 Polymer‐Immobilized Chiral N‐Heterocyclic Carbenes......Page 71
  2.3.2 Au: Polymer‐Immobilized Triazole–Gold Catalyst......Page 72
  2.3.3 Co: Polymer‐Immobilized Co(III)–Salen Complex......Page 73
  2.3.4 Ir: Polymer‐Immobilized Iridium Catalyst......Page 74
  2.3.5 Mo: Polymer‐Immobilized Molybdenum Catalyst......Page 76
  2.3.6 Ni: Polymer‐Immobilized Ni Catalyst......Page 77
  2.3.7 Pd: Polymer‐Immobilized Pd Catalyst......Page 78
  2.3.8 Pt: Polymer‐Immobilized Pt Nanoparticle......Page 80
  2.3.9 Rh: Polymer‐Immobilized Rh Catalyst......Page 81
  2.3.10 Ru: Polymer‐Immobilized Ru Catalyst......Page 84
  2.3.11 Ti: Polymer‐Immobilized Ti Catalyst......Page 85
  2.3.12 Zn: Polymer‐Immobilized Zn Catalyst......Page 86
 List of Abbreviations......Page 87
 References......Page 88
 3.1 Introduction......Page 93
  3.2.1 Organocatalysis......Page 94
  3.2.2 Organometallic Catalysis......Page 98
 3.3 Carbon Nanotubes‐Based Catalysts......Page 103
  3.3.1 Supramolecular Functionalization......Page 104
   3.3.2.1 Organocatalysis......Page 108
   3.3.2.2 Organometallic Catalysis......Page 109
 3.4 Graphene‐Based Catalysts......Page 115
  3.4.1 Supramolecular Functionalization......Page 116
   3.4.2.1 Organocatalysis......Page 118
   3.4.2.2 Organometallic Catalysis......Page 121
 3.5 Outlook and Perspectives: Conclusions......Page 125
 List of Abbreviations......Page 126
 References......Page 127
 4.1 Introduction......Page 131
 4.2 Structure and Properties of the Nanocatalysts......Page 133
   4.2.1.1 MNP and Catalyst......Page 134
   4.2.1.2 Structure Type I......Page 135
   4.2.1.3 Structure Type II......Page 137
   4.2.1.4 Other Structure Types......Page 138
  4.2.2 A Few Points About Synthesis......Page 139
  4.2.3 Magnetic Recovery......Page 142
  4.2.4 Recycling......Page 144
 4.3 Characterization of the Nanocatalysts......Page 145
  4.3.1 Morphology and Crystal Structure......Page 146
  4.3.2 Magnetic Properties......Page 147
  4.3.3 Identification of the Supported Species......Page 148
  4.3.4 Catalyst Loading and Leaching......Page 151
  4.3.5 DLS and Z‐potential......Page 152
 4.4 Stereoselective Reactions......Page 153
  4.4.1 Substitutions......Page 154
  4.4.2 Condensations......Page 155
  4.4.3 Additions......Page 157
  4.4.4 Hydrogenations and Reductions......Page 162
  4.4.5 Epoxidations and Oxidations......Page 164
  4.4.6 Carbon–Carbon Couplings......Page 166
  4.4.7 Kinetic Resolution of Racemic Mixtures......Page 167
 References......Page 170
 5.2 Open Metal Sites as Reaction Sites......Page 175
 5.3 Organic Linkers in the Frameworks as Reaction Sites......Page 178
  5.3.1 Single‐Linker MOFs......Page 179
  5.3.2 Mixed Linker MOFs......Page 180
 5.4 Multifunctional MOFs for Catalysis......Page 182
  5.5.1 Grafting of Active Organic Species on Open Metal Sites......Page 183
  5.5.2 Grafting of Active Functional Groups on Organic Linkers......Page 184
  5.5.3 Grafting of Active Metal Complexes on Functionalized Organic Linkers......Page 186
  5.6.1 Metal/Metal Oxide Nanoparticles on MOFs......Page 189
  5.6.2 Polyoxometalates (POMs)......Page 191
  5.6.3 Metalloporphyrins......Page 192
 5.7 MOF Membranes for Catalysis......Page 193
 Acknowledgments......Page 198
 References......Page 199
 6.1 Introduction......Page 203
  6.2.1 Transition‐Metal Promoted Reaction in Ionic Liquids......Page 205
  6.2.2 Organocatalyzed Transformations Using Ionic Liquids......Page 211
 6.3 Deep Eutectic Solvents (DES) as Reaction Media in Catalysis......Page 215
  6.3.1 Non‐innocent DES as Reaction Media......Page 217
   6.3.2.1 Transition‐Metal Catalyzed Processes......Page 221
   6.3.2.2 Organocatalyzed Reactions......Page 223
 List of Abbreviations......Page 227
 References......Page 228
 7.1 Introduction......Page 233
  7.2.1 Proline Derivatives......Page 235
  7.2.2 Diarylprolinol Derivatives......Page 239
  7.2.3 Imidazolidinones......Page 243
  7.2.4 Primary Amine Organocatalysts......Page 246
  7.2.5 Peptide Catalysts......Page 249
  7.3.1 Ureas and Thioureas......Page 251
  7.3.2 Squaramides......Page 254
  7.3.3 Amides and Sulfonamides......Page 256
 7.4 Immobilized Chiral Phosphoric Acids......Page 257
 7.5 Immobilized Lewis and Brønsted Base Organocatalysts......Page 260
  7.5.2 Isothioureas......Page 261
  7.5.4 Brønsted Bases......Page 263
 7.6 Immobilized Phase Transfer Catalysts......Page 265
 7.7 Final Remarks and Future Perspectives......Page 266
 References......Page 267
 8.1 Introduction......Page 273
 8.2 Types of Catalytic Flow Reactors and Parameters for Assessing Their Performance......Page 275
 8.3 Soluble Catalytic Systems......Page 276
   8.3.1.1 Organic Solvent Nanofiltration......Page 279
   8.3.1.2 Liquid–Liquid Biphasic Media and Supercritical Fluids......Page 285
   8.3.1.3 SLP Systems......Page 289
  8.3.2 Metal‐Free Catalysts......Page 292
 8.4 Insoluble Catalytic Systems......Page 293
  8.4.1 Packed‐bed CFRs......Page 297
  8.4.2 Monolithic CFRs......Page 298
  8.4.3 Wall‐coated CFRs......Page 300
   8.4.4.1 Reduction Reactions......Page 301
   8.4.4.2 Cross‐Coupling Reactions......Page 305
  8.4.5 Metal‐Free Catalysts......Page 306
 8.5 Conclusions......Page 309
 List of Abbreviations......Page 310
 References......Page 311
 9.1 Introduction......Page 323
 9.2 Inert Membrane Reactor with Mobile Catalysts on the Reaction Side......Page 324
  9.2.1 Organic Solvent Nanofiltration......Page 325
  9.3.1 Hydrogenation Reactions......Page 327
  9.3.2 Carbon–Carbon (C–C) Cross‐couplings......Page 328
 9.5 Photocatalytic Organic Synthesis and Their Utilization in the Reduction of Organic Pollutant in Membrane Reactors......Page 329
  9.5.2 Membrane Reactors with Suspending Catalyst in the Reaction Mixture......Page 330
 9.6 The Applications of Membrane Reactors in the Biodiesel Transesterification......Page 332
 List of Abbreviations......Page 336
 References......Page 337
 10.1 Introduction......Page 341
  10.2.1 Background......Page 342
   10.2.2.1 Suzuki Coupling Reaction......Page 343
   10.2.2.2 Hiyama Coupling Reaction......Page 346
   10.2.2.3 Ullmann Coupling Reaction......Page 349
   10.2.2.4 Heck Reaction......Page 350
   10.2.2.5 Copper‐Free Sonogashira Coupling Reaction......Page 351
   10.2.2.6 One‐Pot Synthesis of Dibenzyls and 3‐Arylpropanoic Acids......Page 353
   10.2.3.1 Aerobic Oxidation of Alcohols......Page 354
   10.2.3.2 Hydrogen‐Transfer Reduction in the Presence of Polystyrene‐Stabilized Platinum Nanoparticles......Page 356
  10.3.1 Background......Page 357
  10.3.2 Aqueous Aerobic Flow Oxidation of Alcohols by Amphiphilic Resin‐Dispersed Particles of Platinum (ARP‐Pt)......Page 358
  10.3.3 Flow Hydrogenation of Olefins, Nitrobenzenes, and Aldehydes by Amphiphilic Resin‐Dispersed Particles of Platinum (ARP‐Pt)......Page 365
  10.3.4 Flow Hydrogenation by Amphiphilic Resin‐Dispersed Particles of Iron (ARP‐Fe)......Page 368
  10.3.5 Aqueous Huisgen 1,3‐Cycloaddition with an Amphiphilic Resin‐Supported Triazine‐Based Polyethyleneamine Dendrimer–Copper Catalyst......Page 372
  10.3.6 Aqueous Asymmetric 1,4‐Addition with an Amphiphilic Resin‐Supported Chiral Diene–Rhodium Complex......Page 375
 List of Abbreviations......Page 379
 References......Page 380
 11.1 Introduction......Page 385
 11.2 3D Printing......Page 387
  11.2.1 Fuse Deposition Modeling (FDM)......Page 389
  11.2.2 Millifluidic and Flow Reactors......Page 390
  11.2.3 Catalysts Embedded Thermoplastics......Page 392
  11.2.4 Resin Printers......Page 398
  11.2.5 Robocasting (Direct Ink Writing)......Page 404
  11.2.6 Powder Bed Fusion Printers......Page 412
 11.3 Conclusion......Page 415
 List of Abbreviations......Page 418
 References......Page 419
 12.1 Introduction......Page 425
 12.2 Physical Immobilization Methodologies......Page 426
  12.2.2 Encapsulation......Page 427
  12.3.1 Non‐covalent Bonding......Page 429
   12.3.1.1 Hydrophobic Adsorption......Page 430
   12.3.1.2 Ionic Exchange Adsorption......Page 431
  12.3.2 Covalent Bonding......Page 434
 List of Abbreviations......Page 442
 References......Page 443
 13.1 Introduction: The Quest for Chemicals and the Role of Organic Synthesis......Page 453
 13.2 Enzymes as Enablers of Synthesis......Page 457
 13.3 Enzymes in Action: Immobilized Processes on Scale......Page 460
 13.4 Key Features of Systems Operating with Immobilized Enzymes......Page 468
 13.5 Future Perspectives: The Road Ahead......Page 473
 List of Abbreviations......Page 475
 References......Page 476
Index......Page 481
EULA......Page 494