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Supported Ionic Liquids. Fundamentals and Applications - Product Image

Supported Ionic Liquids. Fundamentals and Applications

  • Published: January 2014
  • 496 Pages
  • John Wiley and Sons Ltd

This unique book gives a timely overview about the fundamentals and applications of supported ionic liquids in modern organic synthesis. It introduces the concept and synthesis of SILP materials and presents important applications in the field of catalysis (e.g. hydroformylation, hydrogenation, coupling reactions, fine chemical synthesis) as well as energy technology and gas separation. Written by pioneers in the field, this book is an invaluable reference book for organic chemists in academia or industry.

Preface XV

List of Contributors XVII

1 Introduction 1
Rasmus Fehrmann, Marco Haumann, and Anders Riisager

1.1 A Century of Supported Liquids 1

1.2 Supported Ionic Liquids 2

1.3 Applications in Catalysis 5

1.4 Applications in Separation 5

1.5 Coating of Heterogeneous Catalysts 6

1.6 Monolayers of IL on Surfaces 7

1.7 Conclusion 7

References 8

Part I Concept and Building Blocks 11

2 Introducing Ionic Liquids 13
Tom Welton

2.1 Introduction 13

2.2 Preparation 13

2.3 Liquid Range 14

2.4 Structures 16

2.4.1 The Liquid/Solid Interface 17

2.4.2 The Liquid/Gas Interface 19

2.5 Physical Properties 20

2.5.1 The Liquid/Solid Interface 21

2.5.2 The Liquid/Gas Interface 21

2.5.3 Polarity 22

2.5.4 Chromatographic Measurements and the Abraham Model of Polarity 24

2.5.5 Infinite Dilution Activity Coefficients 24

2.6 Effects of Ionic Liquids on Chemical Reactions 26

2.7 Ionic Liquids as Process Solvents in Industry 29

2.8 Summary 30

References 31

3 Porous Inorganic Materials as Potential Supports for Ionic Liquids 37
Wilhelm Schwieger, Thangaraj Selvam, Michael Klumpp, and Martin Hartmann

3.1 Introduction 37

3.2 Porous Materials – an Overview 39

3.2.1 History 39

3.2.2 Pore Size 40

3.2.3 Structural Aspects 41

3.2.4 Chemistry 43

3.2.5 Synthesis 43

3.3 Silica-Based Materials – Amorphous 48

3.3.1 Silica Gels 48

3.3.2 Precipitated Silicas 49

3.3.3 Porous Glass 49

3.4 Layered Materials 51

3.5 Microporous Materials 52

3.5.1 Zeolites 52

3.5.2 AlPOs/SAPOs 54

3.5.3 Hierarchical Porosity in Zeolite Crystals 55

3.6 Ordered Mesoporous Materials 56

3.6.1 Silica-Based Classical Compounds 58

3.6.2 PMOs 60

3.6.3 Mesoporous Carbons 61

3.6.4 Other Mesoporous Oxides 61

3.6.5 Anodic Oxidized Materials 62

3.7 Structured Supports and Monolithic Materials 63

3.7.1 Monoliths with Hierarchical Porosity 64

3.7.2 Hierarchically Structured Reactors 65

3.8 Conclusions 66

References 66

4 Synthetic Methodologies for Supported Ionic Liquid Materials 75
Reinout Meijboom, Marco Haumann, Thomas E. M¨uller, and Normen Szesni

4.1 Introduction 75

4.2 Support Materials 76

4.3 Preparation Methods for Supported Ionic Liquids 77

4.3.1 Incipient Wetness Impregnation 77

4.3.2 Freeze-Drying 79

4.3.3 Spray Coating 80

4.3.4 Chemically Bound Ionic Liquids 82

4.3.5 IL–Silica Hybrid Materials 89

4.4 Summary 91

References 91

Part II Synthesis and Properties 95

5 Pore Volume and Surface Area of Supported Ionic Liquids Systems 97
Florian Heym, Christoph Kern, Johannes Thiessen, and Andreas Jess

5.1 Example I: [EMIM][NTf2] on Porous Silica 98

5.2 Example II: SCILL Catalyst (Commercial Ni catalyst) Coated with [BMIM][OcSO4] 99

Acknowledgments 103

Symbols 104

Abbreviations 104

References 104

6 Transport Phenomena, Evaporation, and Thermal Stability of Supported Ionic Liquids 105
Florian Heym, Christoph Kern, Johannes Thiessen, and Andreas Jess

6.1 Introduction 105

6.2 Diffusion of Gases and Liquids in ILs and Diffusivity of ILs in Gases 106

6.2.1 Diffusivity of Gases and Liquids in ILs 106

6.2.2 Diffusion Coefficient of Evaporated ILs in Gases 108

6.3 Thermal Stability and Vapor Pressure of Pure ILs 109

6.3.1 Drawbacks and Opportunities Regarding Stability and Vapor Pressure Measurements of ILs 109

6.3.2 Experimental Methods to Determine the Stability and Vapor Pressure of ILs 110

6.3.3 Data Evaluation and Modeling Methodology 110

6.3.3.1 Evaluation of Vapor Pressure and Decomposition of ILs by Ambient Pressure TG at Constant Heating Rate 110

6.3.3.2 Evaluation of Vapor Pressure of ILs by High Vacuum TG 114

6.3.4 Vapor Pressure Data and Kinetic Parameters of Decomposition of Pure ILs 116

6.3.4.1 Kinetic Data of Thermal Decomposition of Pure ILs 116

6.3.4.2 Vapor Pressure of Pure ILs 116

6.3.5 Guidelines to Determine the Volatility and Stability of ILs 118

6.3.6 Criteria for the Maximum Operation Temperature of ILs 118

6.3.6.1 Maximum Operation Temperature of ILs with Regard to Thermal Decomposition 118

6.3.6.2 Maximum Operation Temperature of ILs with Regard to Evaporation 120

6.4 Vapor Pressure and Thermal Decomposition of Supported ILs 120

6.4.1 Thermal Decomposition of Supported ILs 121

6.4.2 Mass Loss of Supported ILs by Evaporation 123

6.4.2.1 Evaporation of ILs Coated on Silica (SILP-System) 123

6.4.2.2 Evaporation of ILs Coated on a Ni-Catalyst (SCILL-System) 132

6.4.2.3 Evaluation of Internal Surface Area by the Evaporation Rate of Supported ILs 132

6.4.3 Criteria for the Maximum Operation Temperature of Supported ILs 134

6.4.3.1 Maximum Operation Temperature of Supported ILs with Regard to Thermal Stability 134

6.4.3.2 Maximum Operation Temperature of Supported ILs with Regard to Evaporation 135

6.5 Outlook 137

Acknowledgments 138

Symbols 138

Abbreviations 140

References 140

7 Ionic Liquids at the Gas–Liquid and Solid–Liquid Interface – Characterization and Properties 145
Zlata Grenoble and Steven Baldelli

7.1 Introduction 145

7.2 Characterization of Ionic Liquid Surfaces by Spectroscopic Techniques 146

7.2.1 Types of Interfacial Systems Involving Ionic Liquids 146

7.2.2 Overview of Surface Analytical Techniques for Characterization of Ionic Liquids 146

7.2.3 Structural and Orientational Analysis of Ionic Liquids at the Gas–Liquid Interface 147

7.2.3.1 Principles of Sum-Frequency Vibrational Spectroscopy 147

7.2.4 Cation-Specific Ionic Liquid Orientational Analysis 148

7.2.5 Anion-Specific Ionic Liquid Orientational Analysis 154

7.2.6 Ionic Liquid Interfacial Analysis by Other Surface-Specific Techniques 157

7.2.7 Ionic Liquid Effects on Surface Tension 162

7.2.8 Ionic Liquid Effects on Surface Charge Density 163

7.3 Orientation and Properties of Ionic Liquids at the Solid–Liquid Interface 165

7.3.1 Surface Orientational Analysis of Ionic Liquids on Dry Silica 165

7.3.2 Cation Orientational Analysis 166

7.3.3 Alkyl Chain Length Effects on Orientation 167

7.3.4 Competing Anions and Co-adsorption 168

7.3.5 Computational Simulations of Ionic Liquid on Silica 168

7.3.6 Ionic Liquids on Titania (TiO2) 170

7.4 Comments 172

References 173

8 Spectroscopy on Supported Ionic Liquids 177
Peter S. Schulz

8.1 NMR-Spectroscopy 178

8.1.1 Spectroscopy of Support and IL 178

8.1.2 Spectroscopy of the Catalyst 183

8.2 IR Spectroscopy 186

References 189

9 A Priori Selection of the Type of Ionic Liquid 191
Wolfgang Arlt and Alexander Buchele

9.1 Introduction and Objective 191

9.2 Methods 191

9.2.1 Experimental Determination of Gas Solubilities 192

9.2.1.1 Magnetic Suspension Balance 192

9.2.1.2 Isochoric Solubility Cell 194

9.2.1.3 Inverse Gas Chromatography 195

9.2.2 Prediction of Gas Solubilities with COSMO-RS 196

9.2.3 Reaction Equilibrium and Reaction Kinetics 197

9.3 Usage of COSMO-RS to Predict Solubilities in IL 198

9.4 Results of Reaction Modeling 201

9.5 Perspectives of the A Priori Selection of ILs 202

References 205

Part III Catalytic Applications 209

10 Supported Ionic Liquids as Part of a Building-Block System for Tailored Catalysts 211
Thomas E. M¨uller

10.1 Introduction 211

10.2 Immobilized Catalysts 212

10.3 Supported Ionic Liquids 214

10.4 The Building Blocks 215

10.4.1 Ionic Liquid 215

10.4.2 Support 216

10.4.3 Catalytic Function 218

10.4.3.1 Type A1 – Task Specific IL 219

10.4.3.2 Type A2 – Immobilized Homogeneous Catalysts and Metal Nanoparticles 219

10.4.3.3 Type B – Heterogeneous Catalysts Coated with IL 221

10.4.3.4 Type C – Chemically Bound Monolayers of IL 221

10.4.4 Additives and Promoters 222

10.4.5 Preparation and Characterization of Catalysts Involving Supported ILs 222

10.5 Catalysis in Supported Thin Films of IL 222

10.6 Supported Films of IL in Catalysis 223

10.6.1 Hydrogenation Reactions 224

10.6.2 Hydroamination 225

10.7 Advantages and Drawbacks of the Concept 228

10.8 Conclusions 229

Acknowledgments 229

References 229

11 Coupling Reactions with Supported Ionic Liquid Catalysts 233
Zhenshan Hou and Buxing Han

11.1 Introduction 233

11.2 A Short History of Supported Ionic Liquids 234

11.3 Properties of SIL 234

11.4 Application of SIL in Coupling Reactions 235

11.4.1 C–C Coupling Reactions 235

11.4.1.1 Stille Cross Coupling Reactions 235

11.4.1.2 Friedel–Crafts Alkylation 235

11.4.1.3 Olefin Hydroformylation Reaction 236

11.4.1.4 Methanol Carbonylation 237

11.4.1.5 Suzuki Coupling Reactions 237

11.4.1.6 Heck Coupling Reactions 239

11.4.1.7 Diels–Alder Cycloaddition 241

11.4.1.8 Mukaiyama reaction 242

11.4.1.9 Biglinelli Reaction 242

11.4.1.10 Olefin Metathesis Reaction 243

11.4.2 C–N Coupling Reaction 243

11.4.2.1 Hydroamination 243

11.4.2.2 N-Arylation of N-Containing Heterocycles 244

11.4.2.3 Huisgen [3+2] Cycloaddition 244

11.4.3 Miscellaneous Coupling Reaction 244

11.5 Conclusion 246

References 246

12 Selective Hydrogenation for Fine Chemical Synthesis 251
Pasi Virtanen, Eero Salminen, P¨aivi M¨aki-Arvela, and Jyri-Pekka Mikkola

12.1 Introduction 251

12.2 Selective Hydrogenation of a,ß-Unsaturated Aldehydes 251

12.3 Asymmetric Hydrogenations over Chiral Metal Complexes Immobilized in SILCAs 257

12.4 Conclusions 261

References 261

13 Hydrogenation with Nanoparticles Using Supported Ionic Liquids 263
Jackson D. Scholten and Jairton Dupont

13.1 Introduction 263

13.2 MNPs Dispersed in ILs: Green Catalysts for Multiphase Reactions 264

13.3 MNPs Immobilized on Supported Ionic Liquids: Alternative Materials for Catalytic Reactions 267

13.4 Conclusions 275

References 275

14 Solid Catalysts with Ionic Liquid Layer (SCILL) 279
Wolfgang Korth and Andreas Jess

14.1 Introduction 279

14.2 Classification of Applications of Ionic Liquids in Heterogeneous Catalysis 280

14.3 Preparation and Characterization of the Physical Properties of the SCILL Systems 283

14.3.1 Preparation of SCILL Catalysts 283

14.3.2 Nernst Partition Coefficients 284

14.3.3 Pore Volume and Surface Area of the SCILL Catalyst with [BMIM][OcSO4] as IL 287

14.4 Kinetic Studies with SCILL Catalysts 287

14.4.1 Experimental 287

14.4.2 Hydrogenation of 1,5-Cyclooctadiene (COD) 288

14.4.2.1 Reaction Steps of 1,5-COD Hydrogenation on the Investigated Ni Catalyst 288

14.4.2.2 Influence of ILCoating of the Ni Catalyst on the Selectivity of COD Hydrogenation 288

14.4.2.3 Influence of IL Coating of the Catalyst on the Rate of COD Hydrogenation 291

14.4.2.4 Influence of Pore Diffusion on the Effective Rate of COD Hydrogenation 293

14.4.2.5 Influence of Pore Diffusion on the Selectivity of COD Hydrogenation 295

14.4.2.6 Stability of the IL Layer and Deactivation of IL-Coated Catalyst 297

14.4.3 Hydrogenation of Octine, Cinnamaldehyde, and Naphthalene with SCILL Catalysts 297

14.4.4 Hydrogenation of Citral with SCILL Catalysts 298

14.5 Conclusions and Outlook 300

Acknowledgments 300

Symbols Used 300

Greek Symbols 301

Abbreviations and Subscripts 301

References 302

15 Supported Ionic Liquid Phase (SILP) Materials in Hydroformylation Catalysis 307
Andreas Sch¨onweiz and Robert Franke

15.1 SILP Materials in Liquid-Phase Hydroformylation Reactions 307

15.2 Gas-Phase SILP Hydroformylation Catalysis 311

15.3 SILP Combined with scCO2 – Extending the Substrate Range 319

15.4 Continuous SILP Gas-Phase Methanol Carbonylation 322

15.5 Conclusion and Future Potential 323

References 324

16 Ultralow Temperature Water–Gas Shift Reaction Enabled by Supported Ionic Liquid Phase Catalysts 327
Sebastian Werner and Marco Haumann

16.1 Introduction to Water–Gas Shift Reaction 327

16.1.1 Heterogeneous WGS Catalysts 327

16.1.2 Homogeneous WGS Catalysts 329

16.2 Challenges 332

16.3 SILP Catalyst Development 332

16.4 Building-Block Optimization 333

16.4.1 Catalyst Precursor 334

16.4.2 Support Material 335

16.4.3 IL Variation 337

16.4.4 Catalyst Loading 338

16.4.5 IL Loading 339

16.4.6 Combination of Optimized Parameters 340

16.5 Application-Specific Testing 341

16.5.1 Restart Behavior 341

16.5.2 Industrial Support Materials 343

16.5.3 Elevated Pressure 345

16.5.4 Reformate Synthesis Gas Tests 346

16.6 Conclusion 348

References 348

17 Biocatalytic Processes Based on Supported Ionic Liquids 351
Eduardo Garc´?a-Verdugo, Pedro Lozano, and Santiago V. Luis

17.1 Introduction and General Concepts 351

17.1.1 Enzymes and Ionic Liquids 351

17.1.2 Supported ILs for Biocatalytic Processes 353

17.1.3 Reactor Configurations with Supported ILs for Biocatalytic Processes 355

17.2 Biocatalysts Based on Supported Ionic Liquid Phases (SILPs) 356

17.3 Biocatalysts Based on Covalently Supported Ionic Liquid-Like Phases (SILLPs) 360

17.4 Conclusions/Future Trends and Perspectives 365

Acknowledgments 365

References 365

18 Supported Ionic Liquid Phase Catalysts with Supercritical Fluid Flow 369
Rub´en Duque and David J. Cole-Hamilton

18.1 Introduction 369

18.2 SILP Catalysis 369

18.2.1 Liquid-Phase Reactions 369

18.2.2 Gas-Phase Reactions 370

18.2.3 Supercritical Fluids 371

18.2.4 SCF IL Biphasic Systems 372

18.2.5 SILP Catalysis with Supercritical Flow 375

References 381

Part IV Special Applications 385

19 Pharmaceutically Active Supported Ionic Liquids 387
O. Andreea Cojocaru, Amal Siriwardana, Gabriela Gurau, and Robin D. Rogers

19.1 Active Pharmaceutical Ingredients in Ionic Liquid Form 387

19.2 Solid-Supported Pharmaceuticals 389

19.3 Silica Materials for Drug Delivery 389

19.4 Factors That Influence the Loading and Release Rate of Drugs 391

19.4.1 Adsorptive Properties (Pore Size, Surface Area, Pore Volume) of Mesoporous Materials 391

19.4.1.1 Pore Size 391

19.4.1.2 Surface Area 392

19.4.1.3 Pore Volume 392

19.4.2 Surface Functionalization of Mesoporous materials 392

19.4.3 Drug Loading Procedures 394

19.4.3.1 Covalent Attachment 394

19.4.3.2 Physical Trapping 394

19.4.3.3 Adsorption 395

19.5 SILPs Approach for Drug Delivery 395

19.5.1 ILs Confined on Silica 395

19.5.2 API-ILs Confined on Silica 396

19.5.2.1 Synthesis and Characterization of SILP Materials 396

19.5.2.2 Release Studies of the API-ILs from the SILP Materials 399

19.6 Conclusions 402

References 402

20 Supported Protic Ionic Liquids in Polymer Membranes for Electrolytes of Nonhumidified Fuel Cells 407
Tomohiro Yasuda and Masayoshi Watanabe

20.1 Introduction 407

20.2 Protic ILs as Electrolytes for Fuel Cells 409

20.2.1 Protic ILs 409

20.2.2 Thermal Stability of Protic IL 410

20.2.3 PILs Preferable for Fuel Cell Applications 411

20.3 Membrane Fabrication Including PIL and Fuel Cell Operation 411

20.3.1 Membrane Preparation 411

20.3.2 Fuel Cell Operation Using Supported PILs in Membranes 414

20.4 Proton Conducting Mechanism during Fuel Cell Operation 415

20.5 Conclusion 417

Acknowledgments 418

References 418

21 Gas Separation Using Supported Ionic Liquids 419
Marco Haumann

21.1 SILP Materials 419

21.1.1 SILP-Facilitated GC 423

21.2 Supported Ionic Liquid Membranes (SILMs) 428

21.2.1 Gas Separation 429

21.2.2 Gas Separation and Reaction 437

21.3 Conclusion 440

References 441

22 Ionic Liquids on Surfaces – a Plethora of Applications 445
Thomas J. S. Schubert

22.1 Introduction 445

22.2 The Influence of ILs on Solid-State Surfaces 445

22.3 Layers of ILs on Solid-State Surfaces 446

22.4 Selected Applications 446

22.5 Sensors 447

22.6 Electrochemical Double Layer Capacitors (Supercapacitors) 449

22.7 Dye Sensitized Solar Cells 451

22.8 Lubricants 452

22.9 Synthesis and Dispersions of Nanoparticles 453

References 454

Part V Outlook 457

23 Outlook – the Technical Prospect of Supported Ionic Liquid Materials 459
Peter Wasserscheid

23.1 Competitive Advantage 460

23.2 Observability 462

23.3 Trialability 462

23.4 Compatibility 463

23.5 Complexity 463

23.6 Perceived Risk 464

References 465

Index 467

Rasmus Fehrmann is Professor and head of the Centre for Catalysis and Sustainable Chemistry at the Department of Chemistry, Technical University of Denmark (DTU). After obtaining his PhD from DTU he was awarded university candidate- and senior scholarships as well as postdoctoral fellowships at the Institute of Catalysis in Novosibirsk (Russia), Université de Provence (France), and University of Patras (Greece), before taking up his present appointment. His main scientific achievements fall within the chemistry of sulfuric acid catalysts, environmental catalysis and ionic liquid fundamentals and applications including SLP and SILP technologies. He has authored over 130 scientific publications, 20 patent applications, and 400 oral or poster presentations at international conferences, and has been a board member of the Danish National Committee for Chemistry for over a decade.

Anders Riisager is Associate Professor at the Centre for Catalysis and Sustainable Chemistry at the Department of Chemistry, Technical University of Denmark (DTU). He studied Chemistry at the University of Copenhagen (Denmark) and obtained his PhD in catalysis from DTU in 2002. Subsequently he acquired a three-year postdoctoral fellowship at RWTH-Aachen/University of Erlangen-Nuremberg (Germany) followed by a one-year Villum Kann Rasmussen postdoctoral fellowship at DTU, where he developed novel SILP catalysts and processes. He has authored more than 80 scientific publications and 20 patent applications, and received several honors including a nomination for the Degussa European Science-to-Business Award 2006 for SILP materials. His main scientific focus is the development of sustainable ionic liquid catalysis and separation technology.

Marco Haumann has been a lecturer at the University of Erlangen-Nuremberg (FAU, Germany) since 2003. He studied Engineering and Chemistry at the universities of Dortmund and Berlin (Germany). After obtaining his PhD in 2001, he spent two years at the universities of Cape Town and Johannesburg (South Africa), developing novel catalysts in collaboration with Sasol Technology Pty Limited. From 2011 to the end of 2012, he was in charge of the establishment of the new FAU Branch Campus in Busan, South Korea. He has authored more than 40 scientific publications and was awarded the Arnold-Eucken prize of the Association of German Engineers (VDI-GVC) in 2011 for his contributions on SILP technology. His main scientific focus is the development of novel supported ionic liquid phase materials for catalysis and separation science.

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