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Edited by
Rasmus Fehrmann,
Anders Riisager, and
Marco Haumann
Supported Ionic Liquids

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Edited by
Rasmus Fehrmann,
Anders Riisager, and
Marco Haumann

Supported Ionic Liquids
Fundamentals and Applications

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The Editors
Prof. Dr. Rasmus Fehrmann
Technical University of Denmark
Department of Chemistry
Building 207
2800 Kgs. Lyngby
Denmark
Dr. Anders Riisager
Technical University of Denmark
Department of Chemistry
Building 207
2800 Kgs. Lyngby
Denmark
Dr. Marco Haumann
FAU Erlangen-Năurnberg
LS făur Chem. Reaktionstechnik

Egerlandstr. 3
91058 Erlangen
Germany

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V

Contents
Preface XV
List of Contributors
1

1.1
1.2
1.3
1.4
1.5
1.6
1.7

Introduction 1
Rasmus Fehrmann, Marco Haumann, and Anders Riisager
A Century of Supported Liquids 1
Supported Ionic Liquids 2
Applications in Catalysis 5
Applications in Separation 5
Coating of Heterogeneous Catalysts 6
Monolayers of IL on Surfaces 7
Conclusion 7
References 8
Part I

2
2.1
2.2
2.3
2.4
2.4.1
2.4.2
2.5
2.5.1
2.5.2

2.5.3
2.5.4
2.5.5
2.6
2.7
2.8

XVII

Concept and Building Blocks

11

Introducing Ionic Liquids 13
Tom Welton
Introduction 13
Preparation 13
Liquid Range 14
Structures 16
The Liquid/Solid Interface 17
The Liquid/Gas Interface 19
Physical Properties 20
The Liquid/Solid Interface 21
The Liquid/Gas Interface 21
Polarity 22
Chromatographic Measurements and the Abraham Model of
Polarity 24
Infinite Dilution Activity Coefficients 24
Effects of Ionic Liquids on Chemical Reactions 26
Ionic Liquids as Process Solvents in Industry 29

Summary 30
References 31

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VI

Contents

3

3.1
3.2
3.2.1
3.2.2
3.2.3
3.2.4
3.2.5
3.3
3.3.1
3.3.2
3.3.3
3.4
3.5
3.5.1
3.5.2
3.5.3
3.6
3.6.1

3.6.2
3.6.3
3.6.4
3.6.5
3.7
3.7.1
3.7.2
3.8

4

4.1
4.2
4.3
4.3.1
4.3.2
4.3.3
4.3.4
4.3.5
4.4

Porous Inorganic Materials as Potential Supports for Ionic Liquids
Wilhelm Schwieger, Thangaraj Selvam, Michael Klumpp, and
Martin Hartmann
Introduction 37
Porous Materials – an Overview 39
History 39
Pore Size 40
Structural Aspects 41
Chemistry 43

Synthesis 43
Silica-Based Materials – Amorphous 48
Silica Gels 48
Precipitated Silicas 49
Porous Glass 49
Layered Materials 51
Microporous Materials 52
Zeolites 52
AlPOs/SAPOs 54
Hierarchical Porosity in Zeolite Crystals 55
Ordered Mesoporous Materials 56
Silica-Based Classical Compounds 58
PMOs 60
Mesoporous Carbons 61
Other Mesoporous Oxides 61
Anodic Oxidized Materials 62
Structured Supports and Monolithic Materials 63
Monoliths with Hierarchical Porosity 64
Hierarchically Structured Reactors 65
Conclusions 66
References 66
Synthetic Methodologies for Supported Ionic Liquid Materials
Reinout Meijboom, Marco Haumann, Thomas E. Măuller, and
Normen Szesni
Introduction 75
Support Materials 76
Preparation Methods for Supported Ionic Liquids 77
Incipient Wetness Impregnation 77
Freeze-Drying 79
Spray Coating 80

Chemically Bound Ionic Liquids 82
IL–Silica Hybrid Materials 89
Summary 91
References 91

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75

37


Contents

Part II
5
5.1
5.2

6

6.1
6.2
6.2.1
6.2.2
6.3
6.3.1
6.3.2
6.3.3
6.3.3.1

6.3.3.2
6.3.4
6.3.4.1
6.3.4.2
6.3.5
6.3.6
6.3.6.1
6.3.6.2
6.4
6.4.1
6.4.2
6.4.2.1
6.4.2.2
6.4.2.3

Synthesis and Properties

95

Pore Volume and Surface Area of Supported Ionic Liquids Systems
Florian Heym, Christoph Kern, Johannes Thiessen, and Andreas Jess
Example I: [EMIM][NTf2 ] on Porous Silica 98
Example II: SCILL Catalyst (Commercial Ni catalyst) Coated with
[BMIM][OcSO4 ] 99
Acknowledgments 103
Symbols 104
Abbreviations 104
References 104

97


Transport Phenomena, Evaporation, and Thermal Stability of Supported
Ionic Liquids 105
Florian Heym, Christoph Kern, Johannes Thiessen, and Andreas Jess
Introduction 105
Diffusion of Gases and Liquids in ILs and Diffusivity of ILs in
Gases 106
Diffusivity of Gases and Liquids in ILs 106
Diffusion Coefficient of Evaporated ILs in Gases 108
Thermal Stability and Vapor Pressure of Pure ILs 109
Drawbacks and Opportunities Regarding Stability and Vapor Pressure
Measurements of ILs 109
Experimental Methods to Determine the Stability and Vapor Pressure
of ILs 110
Data Evaluation and Modeling Methodology 110
Evaluation of Vapor Pressure and Decomposition of ILs by Ambient
Pressure TG at Constant Heating Rate 110
Evaluation of Vapor Pressure of ILs by High Vacuum TG 114
Vapor Pressure Data and Kinetic Parameters of Decomposition of
Pure ILs 116
Kinetic Data of Thermal Decomposition of Pure ILs 116
Vapor Pressure of Pure ILs 116
Guidelines to Determine the Volatility and Stability of ILs 118
Criteria for the Maximum Operation Temperature of ILs 118
Maximum Operation Temperature of ILs with Regard to Thermal
Decomposition 118
Maximum Operation Temperature of ILs with Regard to
Evaporation 120
Vapor Pressure and Thermal Decomposition of Supported ILs 120
Thermal Decomposition of Supported ILs 121

Mass Loss of Supported ILs by Evaporation 123
Evaporation of ILs Coated on Silica (SILP-System) 123
Evaporation of ILs Coated on a Ni-Catalyst (SCILL-System) 132
Evaluation of Internal Surface Area by the Evaporation Rate of
Supported ILs 132

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VII


VIII

Contents

6.4.3
6.4.3.1
6.4.3.2
6.5

7

7.1
7.2
7.2.1
7.2.2
7.2.3
7.2.3.1
7.2.4
7.2.5

7.2.6
7.2.7
7.2.8
7.3
7.3.1
7.3.2
7.3.3
7.3.4
7.3.5
7.3.6
7.4

8
8.1
8.1.1

Criteria for the Maximum Operation Temperature of Supported
ILs 134
Maximum Operation Temperature of Supported ILs with Regard to
Thermal Stability 134
Maximum Operation Temperature of Supported ILs with Regard to
Evaporation 135
Outlook 137
Acknowledgments 138
Symbols 138
Abbreviations 140
References 140
Ionic Liquids at the Gas–Liquid and Solid–Liquid Interface –
Characterization and Properties 145
Zlata Grenoble and Steven Baldelli

Introduction 145
Characterization of Ionic Liquid Surfaces by Spectroscopic
Techniques 146
Types of Interfacial Systems Involving Ionic Liquids 146
Overview of Surface Analytical Techniques for Characterization of
Ionic Liquids 146
Structural and Orientational Analysis of Ionic Liquids at the
Gas–Liquid Interface 147
Principles of Sum-Frequency Vibrational Spectroscopy 147
Cation-Specific Ionic Liquid Orientational Analysis 148
Anion-Specific Ionic Liquid Orientational Analysis 154
Ionic Liquid Interfacial Analysis by Other Surface-Specific
Techniques 157
Ionic Liquid Effects on Surface Tension 162
Ionic Liquid Effects on Surface Charge Density 163
Orientation and Properties of Ionic Liquids at the Solid–Liquid
Interface 165
Surface Orientational Analysis of Ionic Liquids on Dry Silica 165
Cation Orientational Analysis 166
Alkyl Chain Length Effects on Orientation 167
Competing Anions and Co-adsorption 168
Computational Simulations of Ionic Liquid on Silica 168
Ionic Liquids on Titania (TiO2 ) 170
Comments 172
References 173
Spectroscopy on Supported Ionic Liquids
Peter S. Schulz
NMR-Spectroscopy 178
Spectroscopy of Support and IL 178


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177


Contents

8.1.2
8.2

Spectroscopy of the Catalyst 183
IR Spectroscopy 186
References 189

9

A Priori Selection of the Type of Ionic Liquid 191
Wolfgang Arlt and Alexander Buchele
Introduction and Objective 191
Methods 191
Experimental Determination of Gas Solubilities 192
Magnetic Suspension Balance 192
Isochoric Solubility Cell 194
Inverse Gas Chromatography 195
Prediction of Gas Solubilities with COSMO-RS 196
Reaction Equilibrium and Reaction Kinetics 197
Usage of COSMO-RS to Predict Solubilities in IL 198
Results of Reaction Modeling 201
Perspectives of the A Priori Selection of ILs 202
References 205


9.1
9.2
9.2.1
9.2.1.1
9.2.1.2
9.2.1.3
9.2.2
9.2.3
9.3
9.4
9.5

Part III
10

10.1
10.2
10.3
10.4
10.4.1
10.4.2
10.4.3
10.4.3.1
10.4.3.2
10.4.3.3
10.4.3.4
10.4.4
10.4.5
10.5

10.6
10.6.1
10.6.2
10.7
10.8

Catalytic Applications

209

Supported Ionic Liquids as Part of a Building-Block System for Tailored
Catalysts 211
Thomas E. Măuller
Introduction 211
Immobilized Catalysts 212
Supported Ionic Liquids 214
The Building Blocks 215
Ionic Liquid 215
Support 216
Catalytic Function 218
Type A1 – Task Specific IL 219
Type A2 – Immobilized Homogeneous Catalysts and Metal
Nanoparticles 219
Type B – Heterogeneous Catalysts Coated with IL 221
Type C – Chemically Bound Monolayers of IL 221
Additives and Promoters 222
Preparation and Characterization of Catalysts Involving Supported
ILs 222
Catalysis in Supported Thin Films of IL 222
Supported Films of IL in Catalysis 223

Hydrogenation Reactions 224
Hydroamination 225
Advantages and Drawbacks of the Concept 228
Conclusions 229

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IX


X

Contents

Acknowledgments
References 229
11
11.1
11.2
11.3
11.4
11.4.1
11.4.1.1
11.4.1.2
11.4.1.3
11.4.1.4
11.4.1.5
11.4.1.6
11.4.1.7
11.4.1.8

11.4.1.9
11.4.1.10
11.4.2
11.4.2.1
11.4.2.2
11.4.2.3
11.4.3
11.5

12
12.1
12.2
12.3
12.4

13
13.1
13.2
13.3
13.4

229

Coupling Reactions with Supported Ionic Liquid Catalysts
Zhenshan Hou and Buxing Han
Introduction 233
A Short History of Supported Ionic Liquids 234
Properties of SIL 234
Application of SIL in Coupling Reactions 235
C–C Coupling Reactions 235

Stille Cross Coupling Reactions 235
Friedel–Crafts Alkylation 235
Olefin Hydroformylation Reaction 236
Methanol Carbonylation 237
Suzuki Coupling Reactions 237
Heck Coupling Reactions 239
Diels–Alder Cycloaddition 241
Mukaiyama reaction 242
Biglinelli Reaction 242
Olefin Metathesis Reaction 243
C–N Coupling Reaction 243
Hydroamination 243
N-Arylation of N-Containing Heterocycles 244
Huisgen [3+2] Cycloaddition 244
Miscellaneous Coupling Reaction 244
Conclusion 246
References 246

233

Selective Hydrogenation for Fine Chemical Synthesis 251
Pasi Virtanen, Eero Salminen, Păaivi Măaki-Arvela, and Jyri-Pekka Mikkola
Introduction 251
Selective Hydrogenation of α,β-Unsaturated Aldehydes 251
Asymmetric Hydrogenations over Chiral Metal Complexes
Immobilized in SILCAs 257
Conclusions 261
References 261
Hydrogenation with Nanoparticles Using Supported Ionic Liquids 263
Jackson D. Scholten and Jairton Dupont

Introduction 263
MNPs Dispersed in ILs: Green Catalysts for Multiphase
Reactions 264
MNPs Immobilized on Supported Ionic Liquids: Alternative Materials
for Catalytic Reactions 267
Conclusions 275
References 275

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Contents

14
14.1
14.2
14.3
14.3.1
14.3.2
14.3.3
14.4
14.4.1
14.4.2
14.4.2.1
14.4.2.2
14.4.2.3
14.4.2.4
14.4.2.5
14.4.2.6
14.4.3

14.4.4
14.5

15

15.1
15.2
15.3
15.4

Solid Catalysts with Ionic Liquid Layer (SCILL) 279
Wolfgang Korth and Andreas Jess
Introduction 279
Classification of Applications of Ionic Liquids in Heterogeneous
Catalysis 280
Preparation and Characterization of the Physical Properties of the
SCILL Systems 283
Preparation of SCILL Catalysts 283
Nernst Partition Coefficients 284
Pore Volume and Surface Area of the SCILL Catalyst with
[BMIM][OcSO4 ] as IL 287
Kinetic Studies with SCILL Catalysts 287
Experimental 287
Hydrogenation of 1,5-Cyclooctadiene (COD) 288
Reaction Steps of 1,5-COD Hydrogenation on the Investigated Ni
Catalyst 288
Influence of ILCoating of the Ni Catalyst on the Selectivity of COD
Hydrogenation 288
Influence of IL Coating of the Catalyst on the Rate of COD
Hydrogenation 291

Influence of Pore Diffusion on the Effective Rate of COD
Hydrogenation 293
Influence of Pore Diffusion on the Selectivity of COD
Hydrogenation 295
Stability of the IL Layer and Deactivation of IL-Coated
Catalyst 297
Hydrogenation of Octine, Cinnamaldehyde, and Naphthalene with
SCILL Catalysts 297
Hydrogenation of Citral with SCILL Catalysts 298
Conclusions and Outlook 300
Acknowledgments 300
Symbols Used 300
Greek Symbols 301
Abbreviations and Subscripts 301
References 302
Supported Ionic Liquid Phase (SILP) Materials in Hydroformylation
Catalysis 307
Andreas Schăonweiz and Robert Franke
SILP Materials in Liquid-Phase Hydroformylation
Reactions 307
Gas-Phase SILP Hydroformylation Catalysis 311
SILP Combined with scCO2 – Extending the Substrate
Range 319
Continuous SILP Gas-Phase Methanol Carbonylation 322

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XI



XII

Contents

15.5

Conclusion and Future Potential
References 324

16

Ultralow Temperature Water–Gas Shift Reaction Enabled by Supported
Ionic Liquid Phase Catalysts 327
Sebastian Werner and Marco Haumann
Introduction to Water–Gas Shift Reaction 327
Heterogeneous WGS Catalysts 327
Homogeneous WGS Catalysts 329
Challenges 332
SILP Catalyst Development 332
Building-Block Optimization 333
Catalyst Precursor 334
Support Material 335
IL Variation 337
Catalyst Loading 338
IL Loading 339
Combination of Optimized Parameters 340
Application-Specific Testing 341
Restart Behavior 341
Industrial Support Materials 343
Elevated Pressure 345

Reformate Synthesis Gas Tests 346
Conclusion 348
References 348

16.1
16.1.1
16.1.2
16.2
16.3
16.4
16.4.1
16.4.2
16.4.3
16.4.4
16.4.5
16.4.6
16.5
16.5.1
16.5.2
16.5.3
16.5.4
16.6

17
17.1
17.1.1
17.1.2
17.1.3
17.2
17.3

17.4

18

18.1
18.2

323

Biocatalytic Processes Based on Supported Ionic Liquids 351
Eduardo Garc´ıa-Verdugo, Pedro Lozano, and Santiago V. Luis
Introduction and General Concepts 351
Enzymes and Ionic Liquids 351
Supported ILs for Biocatalytic Processes 353
Reactor Configurations with Supported ILs for Biocatalytic
Processes 355
Biocatalysts Based on Supported Ionic Liquid Phases
(SILPs) 356
Biocatalysts Based on Covalently Supported Ionic Liquid-Like Phases
(SILLPs) 360
Conclusions/Future Trends and Perspectives 365
Acknowledgments 365
References 365
Supported Ionic Liquid Phase Catalysts with Supercritical Fluid
Flow 369
Rub´en Duque and David J. Cole-Hamilton
Introduction 369
SILP Catalysis 369

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Contents

18.2.1
18.2.2
18.2.3
18.2.4
18.2.5

Liquid-Phase Reactions 369
Gas-Phase Reactions 370
Supercritical Fluids 371
SCF IL Biphasic Systems 372
SILP Catalysis with Supercritical Flow 375
References 381
Part IV

19

19.1
19.2
19.3
19.4
19.4.1
19.4.1.1
19.4.1.2
19.4.1.3
19.4.2
19.4.3

19.4.3.1
19.4.3.2
19.4.3.3
19.5
19.5.1
19.5.2
19.5.2.1
19.5.2.2
19.6

20

20.1
20.2
20.2.1
20.2.2
20.2.3
20.3
20.3.1
20.3.2

Special Applications

385

Pharmaceutically Active Supported Ionic Liquids 387
O. Andreea Cojocaru, Amal Siriwardana, Gabriela Gurau, and
Robin D. Rogers
Active Pharmaceutical Ingredients in Ionic Liquid Form 387
Solid-Supported Pharmaceuticals 389

Silica Materials for Drug Delivery 389
Factors That Influence the Loading and Release Rate of Drugs 391
Adsorptive Properties (Pore Size, Surface Area, Pore Volume) of
Mesoporous Materials 391
Pore Size 391
Surface Area 392
Pore Volume 392
Surface Functionalization of Mesoporous materials 392
Drug Loading Procedures 394
Covalent Attachment 394
Physical Trapping 394
Adsorption 395
SILPs Approach for Drug Delivery 395
ILs Confined on Silica 395
API-ILs Confined on Silica 396
Synthesis and Characterization of SILP Materials 396
Release Studies of the API-ILs from the SILP Materials 399
Conclusions 402
References 402
Supported Protic Ionic Liquids in Polymer Membranes for Electrolytes
of Nonhumidified Fuel Cells 407
Tomohiro Yasuda and Masayoshi Watanabe
Introduction 407
Protic ILs as Electrolytes for Fuel Cells 409
Protic ILs 409
Thermal Stability of Protic IL 410
PILs Preferable for Fuel Cell Applications 411
Membrane Fabrication Including PIL and Fuel Cell Operation 411
Membrane Preparation 411
Fuel Cell Operation Using Supported PILs in Membranes 414


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XIII


XIV

Contents

20.4
20.5

Proton Conducting Mechanism during Fuel Cell Operation
Conclusion 417
Acknowledgments 418
References 418

21

Gas Separation Using Supported Ionic Liquids 419
Marco Haumann
SILP Materials 419
SILP-Facilitated GC 423
Supported Ionic Liquid Membranes (SILMs) 428
Gas Separation 429
Gas Separation and Reaction 437
Conclusion 440
References 441


21.1
21.1.1
21.2
21.2.1
21.2.2
21.3

22
22.1
22.2
22.3
22.4
22.5
22.6
22.7
22.8
22.9

Ionic Liquids on Surfaces – a Plethora of Applications 445
Thomas J. S. Schubert
Introduction 445
The Influence of ILs on Solid-State Surfaces 445
Layers of ILs on Solid-State Surfaces 446
Selected Applications 446
Sensors 447
Electrochemical Double Layer Capacitors (Supercapacitors) 449
Dye Sensitized Solar Cells 451
Lubricants 452
Synthesis and Dispersions of Nanoparticles 453
References 454

Part V

23

23.1
23.2
23.3
23.4
23.5
23.6

415

Outlook

457

Outlook – the Technical Prospect of Supported Ionic Liquid
Materials 459
Peter Wasserscheid
Competitive Advantage 460
Observability 462
Trialability 462
Compatibility 463
Complexity 463
Perceived Risk 464
References 465
Index

467


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XV

Preface

In recent years, the concept of supported ionic liquids has been utilized as an
innovative and widely applicable technology to design new catalysts, absorbents,
and other functional materials. The technology offers enormous potential to obtain
materials with unique surface properties such as great uniformity, high specificity,
and tunable chemical activity. These materials can show significantly enhanced
efficiencies when applied in processes and products, leading to substantial cost
savings and greatly improved performance. In 2012 a gas purification process
based on 60 tons of supported ionic liquid phase (SILP) absorber material has been
reported by a petrochemical company, constituting the first large-scale application
of this technology in industry.
We anticipate that the concept of ionic liquids on surfaces has great potential
to establish a new and promising field of material science in the future. For
improved material development the profound knowledge of ionic liquid and solid
interactions and the development of sophisticated synthetic methodologies for new
and large-scale production become significant. Reliable characterization methods
as well as a priori tools for fast and efficient selection of the most suitable ionic
liquids are also a key factor in this development. This book addresses these topics
in the first two parts while catalysis with supported ionic liquid material is the focus
of part three. Special applications will be described in part four, including sensor
technology, lubrication, gas purification, and pharmaceuticals.
This book has been written by different authors, being at the forefront of the
particular field, and the reader will find differences in style and notation. We are

convinced that this variety does not harm the scientific impact and that the reader
will be able to get a coherent broad knowledge to this new and exciting research
field.
Copenhagen and Erlangen
October 2013

Rasmus Fehrmann, Anders Riisager,
and Marco Haumann

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XVII

List of Contributors
Wolfgang Arlt
Universităat Erlangen-Năurnberg,
Department of Chemical &
Biochemical engineering (CBI)
Egerlandstr. 3
D-91058 Erlangen
Germany

O. Andreea Cojocaru
The University of Alabama
Center for Green Manufacturing
Department of Chemistry

Tuscaloosa
AL 35487
USA

Steven Baldelli
University of Houston
Department of Chemistry
Houston
TX, 77204-5003
USA

David J. Cole-Hamilton
University of St. Andrews
EaStCHEM
School of Chemistry
St. Andrews, Fife
KY16 9ST, Scotland
United Kingdom

Alexander Buchele
Universităat Erlangen-Năurnberg,
Department of Chemical &
Biochemical engineering (CBI)
Egerlandstr. 3
D-91058 Erlangen
Germany

Jairton Dupont
UFRGS
Laboratory of Molecular Catalysis

Institute of Chemistry
Av. Bento Gonc¸alves, 9500
Porto Alegre 91501-970 RS
Brazil

and
Envi Con & Plant Engineering
GmbH
Am Tullnaupark 15
D-90402 Năurnberg
Germany

Ruben Duque
University of St. Andrews
EaStCHEM
School of Chemistry
St. Andrews, Fife
KY16 9ST, Scotland
United Kingdom

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XVIII

List of Contributors

Rasmus Fehrmann
Technical University of Denmark
Department of Chemistry

Building 207
2800 Kgs. Lyngby
Denmark
Robert Franke
Evonik Industries AG
Paul-Baumann-Str. 1
45772 Marl
Germany

Buxing Han
Beijing National Laboratory for
Molecular Sciences
Institute of Chemistry
Chinese Academy of Sciences
Beijing 100190
China
Martin Hartmann
Erlangen Catalysis Resource
Center
Universităat Erlangen-Năurnberg
Egerlandstr. 3
91058 Erlangen
Germany

and
Lehrstuhl făur Theoretische
Chemie
Ruhr-Universităat Bochum
D-44780 Bochum
Germany


Marco Haumann
FAU Erlangen-Năurnberg
LS făur Chem. Reaktionstechnik
Egerlandstr. 3
91058 Erlangen
Germany

Eduardo Garca-Verdugo
Universitat Jaume I
Departamento de Qumica
Inorganica y Org´anica
Avda. Sos Baynat s/n
E-12071 Castell´on
Spain

Florian Heym
University Bayreuth
Chair of Chemical Engineering
Faculty of Engineering Science
Universităatsstraòe 30
D-95440 Bayreuth
Germany

Zlata Grenoble
University of Houston
Department of Chemistry
Houston
TX 77204-5003
USA

Gabriela Gurau
The University of Alabama
Center for Green Manufacturing
Department of Chemistry
Tuscaloosa
AL 35487
USA

Zhenshan Hou
East China University of Science
and Technology
Key Laboratory for Advanced
Materials
Research Institute of Industrial
Catalysis
No. 130 Meilong Road
Shanghai 200237
China

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List of Contributors

Andreas Jess
University Bayreuth
Chair of Chemical Engineering
Faculty of Engineering Science
D-95440 Bayreuth
Germany

Christoph Kern
University Bayreuth
Chair of Chemical Engineering
Faculty of Engineering Science
D-95440 Bayreuth
Germany
Michael Klumpp
Lehrstuhl făur Chemische
Reaktionstechnik
Universităat Erlangen-Năurnberg
Egerlandstr. 3
91058 Erlangen
Germany
Wolfgang Korth
University Bayreuth
Chair of Chemical Engineering
Faculty of Engineering Science
D-95440 Bayreuth
Germany

Pă
aivi Mă
aki-Arvela

Abo
Akademi University
Process Chemistry Centre
Laboratory of Industrial
Chemistry and Reaction
Engineering

Biskopsgatan 8
˚
FI-20500, Turku/Abo
Finland
Reinout Meijboom
Faculty of Science
Department of Chemistry
University of Johannesburg
Auckland Park
2006 Johannesburg
South Africa
Jyri-Pekka Mikkola
˚
Abo
Akademi University
Process Chemistry Centre
Laboratory of Industrial
Chemistry and Reaction
Engineering
Biskopsgatan 8
˚
FI-20500, Turku/Abo
Finland
and

Pedro Lozano
Universidad de Murcia
Departamento de Bioqu´ımica y
Biolog´ıa Molecular ‘‘B’’ e
Inmunolog´ıa

Facultad de Qu´ımica
Murcia
Spain
Santiago V. Luis
Universitat Jaume I
Departamento de Qu´ımica
Inorg´anica y Org´anica
Avda. Sos Baynat s/n
E-12071 Castell´on
Spain

Umea˚ University
Technical Chemistry
Department of Chemistry
Chemical-Biological Center
Olof Palmes gata 29, SE-90323
Sweden
Thomas E. Mă
uller
CAT Catalytic Center
RWTH Aachen University
Worringerweg 1
52074 Aachen
Germany

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XIX



XX

List of Contributors

Anders Riisager
Technical University of Denmark
Department of Chemistry
Building 207
2800 Kgs. Lyngby
Denmark

Thomas J.S. Schubert
IoLiTec Ionic Liquids
Technologies GmbH
Salzstrasse 184
D-74076 Heilbronn
Germany

Robin D. Rogers
The University of Alabama
Center for Green Manufacturing
Department of Chemistry
Tuscaloosa
AL 35487
USA

Peter S. Schulz
University Erlangen-Nuremberg
Department of Chemical and
Bioengineering

Institute of Chemical Reaction
Engineering
Egerlandstr. 3
91058 Erlangen
Germany

Eero Salminen

Abo
Akademi University

Finland

Wilhelm Schwieger
Lehrstuhl făur Chemische
Reaktionstechnik
Universităat Erlangen-Năurnberg
Egerlandstr. 3
91058 Erlangen
Germany

Jackson D. Scholten
UFRGS
Laboratory of Molecular Catalysis
Institute of Chemistry
Av. Bento Gonc¸alves, 9500
Porto Alegre 91501-970 RS
Brazil

Thangaraj Selvam

Lehrstuhl făur Chemische
Reaktionstechnik
Universităat Erlangen-Năurnberg
Egerlandstr. 3
91058 Erlangen
Germany

Andreas Schă
onweiz
Universităat Erlangen-Năurnberg
Lehrstuhl făur Chemische
Reaktionstechnik
Egerlandstr. 3
91058 Erlangen
Germany

Amal Siriwardana
The University of Alabama
Center for Green Manufacturing
Department of Chemistry
Tuscaloosa
AL 35487
USA

Process Chemistry Centre
Laboratory of Industrial
Chemistry and Reaction
Engineering
Biskopsgatan 8
˚

FI-20500, Turku/Abo

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List of Contributors

Normen Szesni
Clariant Produkte (Deutschland)
GmbH
BU Catalysts
Waldheimer Straòe 13
83052 Bruckmăuhl
Germany
Johannes Thiessen
University Bayreuth
Chair of Chemical Engineering
Faculty of Engineering Science
D-95440 Bayreuth
Germany
Pasi Virtanen
˚
Abo
Akademi University
Process Chemistry Centre
Laboratory of Industrial
Chemistry and Reaction
Engineering
Biskopsgatan 8


FI-20500, Turku/Abo
Finland
Peter Wasserscheid
Universităat Erlangen-Năurnberg
Lehrstuhl făur Chemische
Reaktionstechnik
Egerlandstr. 3
91058 Erlangen
Germany

Tom Welton
Department of Chemistry
Imperial College London
South Kensington Campus
London, SW7 2AZ
United Kingdom
Sebastian Werner
Friedrich-Alexander-Universităat
Erlangen-Năurnberg
Department Chemie- und
Bioingenieurwesen (CBI)
Lehrstuhl făur Chemische
Reaktionstechnik (CRT)
Egerlandstraße 3
D-91058 Erlangen
Germany
Tomohiro Yasuda
Yokohama National University
Cooperative Research and
Development Center

79-5 Tokiwadai
Hodogaya-ku
Yokohama, 240-8501
Japan

Masayoshi Watanabe
Yokohaa National University
Department of Chemistry and
Biotechnology
79-5 Tokiwadai
Hodogaya-ku
Yokohama 240-8501
Japan

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XXI


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1

1
Introduction
Rasmus Fehrmann, Marco Haumann, and Anders Riisager

1.1
A Century of Supported Liquids


Natural and synthesized solid materials are generally characterized by a nonuniform
and undefined surface. The surface contains face atoms, corner atoms, edge atoms,
ad-atoms, and defect sites, which together determine the surface properties of the
material [1]. In many applications, these different sites display different properties,
for example, with respect to their chemical activity. Often, only certain sites are
advantageous with regard to the specific application of the material as in the case
of, heterogeneous catalysts and adsorbents. Future development of more efficient
catalysts and adsorbents in industrial processes will depend on the design of solid
surfaces that allow all surface atoms to be most effective. At the same time, new
technologies are required, which will lead to the design of completely new surface
properties within solids [2].
One possible way to achieve a uniform surface is by coating the solid support
material with a thin liquid film, thereby defining the material properties by the liquid’s properties. Such supported liquid phase (SLP) materials date back a 100 years
ago till 1914, when BASF introduced a silica-supported V2 O5 -alkali/pyrosulfate
SO2 oxidation catalyst for sulfuric acid production (see Figure 1.1) [3]. This catalyst, which is still the standard system for sulfuric acid production today, can be
described as a supported molten salt, as it consists of a mixture of vanadium alkali
sulfate/hydrogensulfate/pyrosulfate complexes that are present under reaction
conditions (400–600 ◦ C) [4].
The concept of supported liquid catalysis is not restricted to liquid salts. In
order to apply the concept of uniform surface properties and efficient catalyst
immobilization, several authors investigated the SLP concept during the 1970s and
1980s [5–11]. However, later studies revealed that the evaporation of the loaded
liquid cannot be avoided completely during operation. This is especially a problem
when using water as the liquid phase [12–17]. In these supported aqueous phase
(SAP) systems, the thin film of water evaporated quickly under reaction conditions,
making the concept applicable only for slurry-phase reactions with hydrophobic
reaction mixtures.
Supported Ionic Liquids: Fundamentals and Applications, First Edition.
Edited by Rasmus Fehrmann, Anders Riisager, and Marco Haumann.

c 2014 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2014 by Wiley-VCH Verlag GmbH & Co. KGaA.

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