Supported Ionic Liquids -- Contents -- Preface -- List of Contributors -- Chapter 1 Introduction -- 1.1 A Century of Supported Liquids -- 1.2 Supported Ionic Liquids -- 1.3 Applications in Catalysis -- 1.4 Applications in Separation -- 1.5 Coating of Heterogeneous Catalysts -- 1.6 Monolayers of IL on Surfaces -- 1.7 Conclusion -- References -- Part I Concept and Building Blocks -- Chapter 2 Introducing Ionic Liquids -- 2.1 Introduction -- 2.2 Preparation -- 2.3 Liquid Range -- 2.4 Structures -- 2.4.1 The Liquid/Solid Interface -- 2.4.2 The Liquid/Gas Interface -- 2.5 Physical Properties -- 2.5.1 The Liquid/Solid Interface -- 2.5.2 The Liquid/Gas Interface -- 2.5.3 Polarity -- 2.5.4 Chromatographic Measurements and the Abraham Model of Polarity -- 2.5.5 Infinite Dilution Activity Coefficients -- 2.6 Effects of Ionic Liquids on Chemical Reactions -- 2.7 Ionic Liquids as Process Solvents in Industry -- 2.8 Summary -- References -- Chapter 3 Porous Inorganic Materials as Potential Supports for Ionic Liquids -- 3.1 Introduction -- 3.2 Porous Materials - an Overview -- 3.2.1 History -- 3.2.2 Pore Size -- 3.2.3 Structural Aspects -- 3.2.4 Chemistry -- 3.2.5 Synthesis -- 3.3 Silica-Based Materials - Amorphous -- 3.3.1 Silica Gels -- 3.3.2 Precipitated Silicas -- 3.3.3 Porous Glass -- 3.4 Layered Materials -- 3.5 Microporous Materials -- 3.5.1 Zeolites -- 3.5.2 AlPOs/SAPOs -- 3.5.3 Hierarchical Porosity in Zeolite Crystals -- 3.6 Ordered Mesoporous Materials -- 3.6.1 Silica-Based Classical Compounds -- 3.6.2 PMOs -- 3.6.3 Mesoporous Carbons -- 3.6.4 Other Mesoporous Oxides -- 3.6.5 Anodic Oxidized Materials -- 3.7 Structured Supports and Monolithic Materials -- 3.7.1 Monoliths with Hierarchical Porosity -- 3.7.2 Hierarchically Structured Reactors -- 3.8 Conclusions -- References.

Chapter 4 Synthetic Methodologies for Supported Ionic Liquid Materials -- 4.1 Introduction -- 4.2 Support Materials -- 4.3 Preparation Methods for Supported Ionic Liquids -- 4.3.1 Incipient Wetness Impregnation -- 4.3.2 Freeze-Drying -- 4.3.3 Spray Coating -- 4.3.4 Chemically Bound Ionic Liquids -- 4.3.5 IL-Silica Hybrid Materials -- 4.4 Summary -- References -- Part II Synthesis and Properties -- Chapter 5 Pore Volume and Surface Area of Supported Ionic Liquids Systems -- 5.1 Example I: [EMIM][NTf2] on Porous Silica -- 5.2 Example II: SCILL Catalyst (Commercial Ni catalyst) Coated with [BMIM][OcSO4] -- Acknowledgments -- Symbols -- Abbreviations -- References -- Chapter 6 Transport Phenomena, Evaporation, and Thermal Stability of Supported Ionic Liquids -- 6.1 Introduction -- 6.2 Diffusion of Gases and Liquids in ILs and Diffusivity of ILs in Gases -- 6.2.1 Diffusivity of Gases and Liquids in ILs -- 6.2.2 Diffusion Coefficient of Evaporated ILs in Gases -- 6.3 Thermal Stability and Vapor Pressure of Pure ILs -- 6.3.1 Drawbacks and Opportunities Regarding Stability and Vapor Pressure Measurements of ILs -- 6.3.2 Experimental Methods to Determine the Stability and Vapor Pressure of ILs -- 6.3.3 Data Evaluation and Modeling Methodology -- 6.3.3.1 Evaluation of Vapor Pressure and Decomposition of ILs by Ambient Pressure TG at Constant Heating Rate -- 6.3.3.2 Evaluation of Vapor Pressure of ILs by High Vacuum TG -- 6.3.4 Vapor Pressure Data and Kinetic Parameters of Decomposition of Pure ILs -- 6.3.4.1 Kinetic Data of Thermal Decomposition of Pure ILs -- 6.3.4.2 Vapor Pressure of Pure ILs -- 6.3.5 Guidelines to Determine the Volatility and Stability of ILs -- 6.3.6 Criteria for the Maximum Operation Temperature of ILs.

6.3.6.1 Maximum Operation Temperature of ILs with Regard to Thermal Decomposition -- 6.3.6.2 Maximum Operation Temperature of ILs with Regard to Evaporation -- 6.4 Vapor Pressure and Thermal Decomposition of Supported ILs -- 6.4.1 Thermal Decomposition of Supported ILs -- 6.4.2 Mass Loss of Supported ILs by Evaporation -- 6.4.2.1 Evaporation of ILs Coated on Silica (SILP-System) -- 6.4.2.2 Evaporation of ILs Coated on a Ni-Catalyst (SCILL-System) -- 6.4.2.3 Evaluation of Internal Surface Area by the Evaporation Rate of Supported ILs -- 6.4.3 Criteria for the Maximum Operation Temperature of Supported ILs -- 6.4.3.1 Maximum Operation Temperature of Supported ILs with Regard to Thermal Stability -- 6.4.3.2 Maximum Operation Temperature of Supported ILs with Regard to Evaporation -- 6.5 Outlook -- Acknowledgments -- Symbols -- Abbreviations -- References -- Chapter 7 Ionic Liquids at the Gas-Liquid and Solid-Liquid Interface - Characterization and Properties -- 7.1 Introduction -- 7.2 Characterization of Ionic Liquid Surfaces by Spectroscopic Techniques -- 7.2.1 Types of Interfacial Systems Involving Ionic Liquids -- 7.2.2 Overview of Surface Analytical Techniques for Characterization of Ionic Liquids -- 7.2.3 Structural and Orientational Analysis of Ionic Liquids at the Gas-Liquid Interface -- 7.2.3.1 Principles of Sum-Frequency Vibrational Spectroscopy -- 7.2.4 Cation-Specific Ionic Liquid Orientational Analysis -- 7.2.5 Anion-Specific Ionic Liquid Orientational Analysis -- 7.2.6 Ionic Liquid Interfacial Analysis by Other Surface-Specific Techniques -- 7.2.7 Ionic Liquid Effects on Surface Tension -- 7.2.8 Ionic Liquid Effects on Surface Charge Density -- 7.3 Orientation and Properties of Ionic Liquids at the Solid-Liquid Interface.

7.3.1 Surface Orientational Analysis of Ionic Liquids on Dry Silica -- 7.3.2 Cation Orientational Analysis -- 7.3.3 Alkyl Chain Length Effects on Orientation -- 7.3.4 Competing Anions and Co-adsorption -- 7.3.5 Computational Simulations of Ionic Liquid on Silica -- 7.3.6 Ionic Liquids on Titania (TiO2) -- 7.4 Comments -- References -- Chapter 8 Spectroscopy on Supported Ionic Liquids -- 8.1 NMR-Spectroscopy -- 8.1.1 Spectroscopy of Support and IL -- 8.1.2 Spectroscopy of the Catalyst -- 8.2 IR Spectroscopy -- References -- Chapter 9 A Priori Selection of the Type of Ionic Liquid -- 9.1 Introduction and Objective -- 9.2 Methods -- 9.2.1 Experimental Determination of Gas Solubilities -- 9.2.1.1 Magnetic Suspension Balance -- 9.2.1.2 Isochoric Solubility Cell -- 9.2.1.3 Inverse Gas Chromatography -- 9.2.2 Prediction of Gas Solubilities with COSMO-RS -- 9.2.3 Reaction Equilibrium and Reaction Kinetics -- 9.3 Usage of COSMO-RS to Predict Solubilities in IL -- 9.4 Results of Reaction Modeling -- 9.5 Perspectives of the A Priori Selection of ILs -- References -- Part III Catalytic Applications -- Chapter 10 Supported Ionic Liquids as Part of a Building-Block System for Tailored Catalysts -- 10.1 Introduction -- 10.2 Immobilized Catalysts -- 10.3 Supported Ionic Liquids -- 10.4 The Building Blocks -- 10.4.1 Ionic Liquid -- 10.4.2 Support -- 10.4.3 Catalytic Function -- 10.4.3.1 Type A1 - Task Specific IL -- 10.4.3.2 Type A2 - Immobilized Homogeneous Catalysts and Metal Nanoparticles -- 10.4.3.3 Type B - Heterogeneous Catalysts Coated with IL -- 10.4.3.4 Type C - Chemically Bound Monolayers of IL -- 10.4.4 Additives and Promoters -- 10.4.5 Preparation and Characterization of Catalysts Involving Supported ILs -- 10.5 Catalysis in Supported Thin Films of IL -- 10.6 Supported Films of IL in Catalysis.

10.6.1 Hydrogenation Reactions -- 10.6.2 Hydroamination -- 10.7 Advantages and Drawbacks of the Concept -- 10.8 Conclusions -- Acknowledgments -- References -- Chapter 11 Coupling Reactions with Supported Ionic Liquid Catalysts -- 11.1 Introduction -- 11.2 A Short History of Supported Ionic Liquids -- 11.3 Properties of SIL -- 11.4 Application of SIL in Coupling Reactions -- 11.4.1 C-C Coupling Reactions -- 11.4.1.1 Stille Cross Coupling Reactions -- 11.4.1.2 Friedel-Crafts Alkylation -- 11.4.1.3 Olefin Hydroformylation Reaction -- 11.4.1.4 Methanol Carbonylation -- 11.4.1.5 Suzuki Coupling Reactions -- 11.4.1.6 Heck Coupling Reactions -- 11.4.1.7 Diels-Alder Cycloaddition -- 11.4.1.8 Mukaiyama reaction -- 11.4.1.9 Biglinelli Reaction -- 11.4.1.10 Olefin Metathesis Reaction -- 11.4.2 C-N Coupling Reaction -- 11.4.2.1 Hydroamination -- 11.4.2.2 N-Arylation of N-Containing Heterocycles -- 11.4.2.3 Huisgen [3+2] Cycloaddition -- 11.4.3 Miscellaneous Coupling Reaction -- 11.5 Conclusion -- References -- Chapter 12 Selective Hydrogenation for Fine Chemical Synthesis -- 12.1 Introduction -- 12.2 Selective Hydrogenation of α,β-Unsaturated Aldehydes -- 12.3 Asymmetric Hydrogenations over Chiral Metal Complexes Immobilized in SILCAs -- 12.4 Conclusions -- References -- Chapter 13 Hydrogenation with Nanoparticles Using Supported Ionic Liquids -- 13.1 Introduction -- 13.2 MNPs Dispersed in ILs: Green Catalysts for Multiphase Reactions -- 13.3 MNPs Immobilized on Supported Ionic Liquids: Alternative Materials for Catalytic Reactions -- 13.4 Conclusions -- References -- Chapter 14 Solid Catalysts with Ionic Liquid Layer (SCILL) -- 14.1 Introduction -- 14.2 Classification of Applications of Ionic Liquids in Heterogeneous Catalysis.

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