Supported Ionic Liquids
Fundamentals and Applications

Preface

INTRODUCTION
A Century of Supported Liquids
Supported Ionic Liquids
Applications in Catalysis
Applications in Separation
Coating of Heerogeneous Catalysts
Monolayers of IL on Surfaces
Conclusion

PART I: Concept and Building Blocks

INTRODUCING IONIC LIQUIDS
Introduction
Preparation
Liquid Range
Structures
Physical Properties
Effects of Ionic Liquids on Chemical Reactions
Ionic Liquids as Process Solvents in Industry
Summary

POROUS INORGANIC MATERIALS AS POTENTIAL SUPPORTS FOR IONIC LIQUIDS
Introduction
Porous Materials -
An Overview
Silica-Based Materials -
Amorphous
Layered Materials
Ordered Mesoporous Materials
Structured Supports and Monolithic Materials
Conclusions

SYNTHETIC METHODOLOGIES FOR SUPPORTED IONIC LIQUID MATERIALS
Introduction
Support Materials
Preparation Methods for Supported Ionic Liquids
Summary

PART II: Synthesis and Properties

PORE VOLUME AND SURFACE AREA OF SUPPORTED IONIC LIQUIDS SYSTEMS
Example I: [EMIM][NTf2] on Porous Silica
Example II: SCILL Catalyst (Commercial Ni catalyst) Coated with [BMIM][OcSO4]

TRANSPORT PHENOMENA, EVAPORATION, AND THERMAL STABILITY OF SUPPORTED IONIC LIQUIDS
Introduction
Diffusion of Gases and Liquids in ILs and Diffusivity of ILs in Gases
Thermal Stability and Vapor Pressure of Pure ILs
Vapor Pressure and Thermal Decomposition of Supported ILs
Outlook

IONIC LIQUIDS AT THE GAS-LIQUID AND SOLID-LIQUID INTERFACE -
CHARACTERIZATION AND PROPERTIES
Introduction
Characterization of Ionic Liquid Surfaces by Spectroscopic Techniques
Orientation and Properties of Ionic Liquids at the Solid-Liquid Interface
Comments

SPECTROSCOPY ON SUPPORTED IONIC LIQUIDS
NMR-Spectroscopy
IR Spectroscopy

A PRIORI SELECTION OF THE TYPE OF IONIC LIQUID
Introduction and Objective
Methods
Usage of COSMO-RS to Predict Solubilities in IL
Results of Reaction Modeling
Perspectives of the A Priori Selection of ILs

PART III: Catalytic Applications

SUPPORTED IONIC LIQUIDS AS PART OF A BUILDING-BLOCK SYSTEM FOR TAILORED CATALYSTS
Introduction
Immobilized Catalysts
Supported Ionic Liquids
The Building Blocks
Catalysis in Supported Thin Films of IL
Supported Films of IL in Catalysis
Advantages and Drawbacks of the Concept
Conclusions

COUPLING REACTIONS WITH SUPPORTED IONIC LIQUID CATALYSTS
Introduction
A Short History of Supported Ionic Liquids
Properties of SIL
Application of SIL in Coupling Reactions
Conclusion

SELECTIVE HYDROGENATION FOR FINE CHEMICAL SYNTHESIS
Introduction
Selective Hydrogenation of Alpha,Beta-Unsaturated Aldehydes
Asymmetric Hydrogenations over Chiral Metal Complexes Immobilize3d in SILCAs
Conclusions

HYDROGENATION WITH NANOPARTICLES USING SUPPORTED IONIC LIQUIDS
Introduction
MNPs Dispersed in ILs: Green Catalysts for Multiphase Reactions
MNPs Immobilized on Supported Ionic Liquids: Alternative Materials for Catalytic Reactions
Conclusions

SOLID CATALYSTS WITH IONIC LIQUID LAYER (SCILL)
Introduction
Classification of Applications of Ionic Liquids in Heterogeneous Catalysis
Preparation and Characterization of the Physical Properties of the SCILL Systems
Kinetic Studies with SCILL Catalysts
Conclusions and Outlook

SUPPORTED IONIC LIQUID PHASE (SILP) MATERIALS IN HYDROFORMYLATION CATALYSIS
SILP Materials in Liquid-Phase Hydroformylation Reactions
Gas-Phase SILP Hydroformylation Catalysis
SILP Combined with scCO2 -
Extending the Substrate Range
Continuous SILP Gas-Phase Methanol Carbonylation
Conclusion and Future Potential

ULTRALOW TEMPERATURE WATER-GAS SHIFT REACTION ENABLED BY SUPPORTED IONIC LIQUID PHASE CATALYSTS
Introduction to Water-Gas Shift Reaction
Challenges
SILP Catalyst Development
Building-Block Optimization
Application-Specific Testing
Conclusion

BIOCATALYTIC PROCESSES BASED ON SUPPORTED IONIC LIQUIDS
Introduction and General Concepts
Biocatalysts Based on Supported Ionic Liquid Phases (SILPs)
Biocatalysts Based on Covalently Supported Ionic Liquid-Like Phases (SILLPs)
Conclusions/Future Trends and Perspectives

SUPPORTED IONIC LIQUID PHASE CATALYSTS WITH SUPERCRITICAL FLUID FLOW
Introduction
SILP Catalysis

PART IV: Special Applications

PHARMACEUTICALLY ACTIVE SUPPORTED IONIC LIQUIDS
Active Pharmaceutical Ingredients in Ionic Liquid Form
Solid-Supported Pharmaceuticals
Silica Materials for Drug Delivery
Factors That Influence the Loading and Release Rate of Drugs
SILPs Approach for Drug Delivery
Conclusions

SUPPORTED PROTIC IONIC LIQUIDS IN POLYMER MEMBRANES FOR ELECTROLYTES OF NONHUMIDIFIED FUEL CELLS
Introduction
Protic ILs as Electrolytes for Fuel Cells
Membrane Fabrication Including PIL and Fuel Cell Operation
Proton Conducting Mechanism during Fuel Cell Operation
Conclusion

GAS SEPARATION USING SUPPORTED IONIC LIQUIDS
SILP Materials
Supported Ionic Liquid Membranes (SILMs)
Conclusion

IONIC LIQUIDS ON SURFACES -
A PLETHORA OF APPLICATIONS
Introduction
The Influence of ILs on Solid-State Surfaces
Layers of ILs on Solid-State Surfaces
Selected Applications
Sensors
Electrochemical Double Layer Capacitors (Supercapacitors)
Dye Sensitized Solar Cells
Lubricants
Synthesis and Dispersions of Nanoparticles

PART V: Outlook

OUTLOOK -
THE TECHNICAL PROSPECT OF SUPPORTED IONIC LIQUID MATERIALS
Competitive Advantage
Observability
Trialability
Compatibility
Complexity
Perceived Risk

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), Universite 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. Professor Fehrmann 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