Ionic Liquids UnCOILed E-Book

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 773

Veröffentlichungsjahr: 2012

Beschreibung

Ionic Liquids UnCOILed presents decisively important reviews on new processes and recent developments in ionic liquid technology with an emphasis on commercial applications in which ionic liquids are replacing, or may replace, processes currently using conventional solvents. Ranging from applied to theoretical, synthetic to analytical, and biotechnological to electrochemical, the book features eleven chapters written by an international group of key academic and industrial chemists, exercising the judicious evaluation which they are uniquely qualified to do. This book is a must for R&D chemists in industrial, governmental and academic laboratories, and for commercial developers of environmentally-friendly, sustainable processes.

Leseprobe

Table of Contents

Cover

Title page

Copyright page

COIL CONFERENCES

PREFACE

ACKNOWLEDGEMENTS

CONTRIBUTORS

ABBREVIATIONS

IONIC LIQUIDS

CATIONS

ANIONS

TECHNIQUES

MISCELLANEOUS

1  Electrodeposition from Ionic Liquids: Interface Processes, Ion Effects, and Macroporous Structures

1.1 INTRODUCTION

1.2 RESULTS AND DISCUSSION

1.3 CONCLUSION

2  Interfaces of Ionic Liquids (1)

2.1 INTRODUCTION

2.2 LIQUID/VACUUM AND LIQUID/GAS INTERFACES

2.3 LIQUID/LIQUID INTERFACES

2.4 SOLID/LIQUID AND ELECTRIFIED SOLID/IONIC FLUID INTERFACES

2.5 WETTING AND ELECTROWETTING CHARACTERISTICS

2.6 SUMMARY AND CONCLUSIONS

ACKNOWLEDGEMENTS

3 Interfaces of Ionic Liquids (2)

3.1 INTRODUCTION

3.2 THE SOLID–IONIC LIQUID INTERFACE

3.3 THE AIR–IONIC LIQUID INTERFACE

3.4 LIQUID–IONIC LIQUID INTERFACES

3.5 FUTURE DIRECTIONS

ACKNOWLEDGEMENTS

4  Ionic Liquids in Separation Science

4.1 BRIEF HISTORY OF THE DEVELOPMENT OF IONIC LIQUIDS AND POLYMERIC IONIC LIQUIDS IN SEPARATION SCIENCE

4.2 IONIC LIQUIDS IN CHROMATOGRAPHIC AND ELECTROPHORETIC SEPARATIONS

4.3 HIGH PERFORMANCE LIQUID CHROMATOGRAPHY

4.4 COUNTER-CURRENT CHROMATOGRAPHY

4.5 IONIC LIQUIDS IN GAS CHROMATOGRAPHY

4.6 IONIC LIQUIDS IN SUPERCRITICAL FLUID CHROMATOGRAPHY

4.7 CAPILLARY ELECTROPHORESIS AND CAPILLARY ELECTROCHROMATOGRAPHY

4.8 PLANAR CHROMATOGRAPHY

4.9 SUMMARY AND FUTURE DIRECTIONS

5 Separation Processes with Ionic Liquids

5.1 INTRODUCTION

5.2 LIQUID SEPARATIONS

5.3 EXTRACTIVE DISTILLATION

5.4 COMBINATION OF SEPARATIONS IN THE LIQUID PHASE WITH MEMBRANES

5.5 GAS SEPARATIONS

5.6 ENGINEERING ASPECTS

5.7 DESIGN OF A SEPARATION PROCESS

5.8 CONCLUSIONS

6 Theoretical Approaches to Ionic Liquids: From Past History to Future Directions

6.1 INTRODUCTION

6.2 VOLUME-BASED APPROACH

6.3 QUANTITATIVE STRUCTURE–PROPERTY RELATIONSHIP METHODS

6.4 MOLECULAR DYNAMICS SIMULATIONS

6.5 APPROACHES FROM FIRST PRINCIPLES BASED ON ab initio AND DENSITY FUNCTIONAL THEORY

6.6 Ab initio MD SIMULATIONS

6.7 OUTLOOK: TOWARDS LARGE-SCALE CALCULATIONS OF IONIC LIQUIDS FROM FIRST PRINCIPLES

7  Ionic Liquids Derived from Natural Sources

7.1 INTRODUCTION

7.2 SYNTHESIS OF AMINO ACID IONIC LIQUIDS

7.3 PHYSICOCHEMICAL PROPERTIES

7.4 AMINO ACID IONIC LIQUIDS CONTAINING DERIVATISED AMINO ACIDS

7.5 APPLICATION OF AMINO ACID IONIC LIQUIDS

7.6 CONCLUSION

ACKNOWLEDGEMENTS

8  Ionic Liquids Studied at Ultra-High Vacuum

8.1 INTRODUCTION

8.2 THE VAPOUR PHASE

8.3 THE CONDENSED PHASE

8.4 CONCLUSIONS AND OPPORTUNITIES FOR THE FUTURE

9  Pioneering Biological Processes in the Presence of Ionic Liquids: The Potential of Filamentous Fungi

9.1 INTRODUCTION

9.2 TOLERANCE OF FILAMENTOUS FUNGI TO IONIC LIQUIDS

9.3 IONIC LIQUID BIODEGRADATION BY FILAMENTOUS FUNGI

9.4 THE IMPACT OF IONIC LIQUIDS ON THE METABOLISM OF FILAMENTOUS FUNGI

9.5 CONCLUDING REMARKS

ACKNOWLEDGEMENTS

10  Use of Ionic Liquids in Dye-Sensitised Solar Cells

10.1 INTRODUCTION

10.2 IONIC LIQUIDS FOR QUASI-SOLID STATE DSSCs

10.3 VARIATIONS FROM “TRADITIONAL” DSSC STRUCTURES

10.4 CONCLUSIONS AND FUTURE DIRECTIONS

11  Phase Behaviour of Gases in Ionic Liquids

11.1 INTRODUCTION

11.2 EXPERIMENTAL TECHNIQUES

11.3 MODELLING GAS SOLUBILITY

11.4 TERNARY PHASE BEHAVIOUR

11.5 NEW DIRECTIONS

11.6 CONCLUDING REMARKS

ACKNOWLEDGEMENTS

Index

Cover Image: Courtesy of Kenneth Seddon, Natalia Plechkova, and Ian Gibson

Copyright © 2013 by John Wiley & Sons, Inc. All rights reserved

Published by John Wiley & Sons, Inc., Hoboken, New Jersey

Published simultaneously in Canada

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Library of Congress Cataloging-in-Publication Data:

Ionic liquids uncoiled : critical expert overviews / edited by Natalia V. Plechkova, Kenneth R. Seddon.

p. cm.

 Summary: “The book presents articles on topics at the forefront of ionic liquids research, ranging from applied to theoretical, from synthetic to analytical, from biotechnology to electrochemistry, from process engineering to nanotechnology”—Provided by publisher.

 Includes bibliographical references and index.

 ISBN 978-0-470-07470-1 (hardback)

 1. Ionic solutions. 2. Ionic structure. I. Plechkova, Natalia V., 1979– II. Seddon, Kenneth R., 1950–

 QD541.I56 2012

 541'.3723–dc23

2012020575

COIL CONFERENCES

PREFACE

So, why the strange title for this book? Is this just a book of conference proceedings based on lectures at COIL? How is this book different from the series of volumes that were edited with Prof. Robin D. Rogers based on symposia we had organised at American Chemical Society (ACS) meetings? We will attempt here to answer these questions, and others, and hence explain the philosophy behind this book.

COIL (Congress on Ionic Liquids) was a concept that originally arose in discussions with DeChema, following on from a meeting about the Green Solvents series of conferences, which have traditionally been held in Germany. It was noticed that the number of submitted papers on ionic liquids surpassed the total of all the other papers combined. At that time, the only international meeting on ionic liquids had been a NATO Workshop, held in Crete in 2000 (Rogers, R.D., Seddon, K.R., and Volkov, S. (eds.), Green industrial applications of ionic liquids, NATO Science Series II: Mathematics, Physics and Chemistry, Vol. 92, Kluwer, Dordrecht, 2002). This was correctly interpreted as a need for a truly dedicated international meeting on ionic liquids, and so COIL was born. With the invaluable support of DeChema, the first meeting was held in Salzburg (literally, and appropriately, “Salt Castle”), and it has since moved around the world biannually, in a carefully planned progression. These meetings have been a resounding success, and their timeline is given on the opposite page. It is, unquestionably, the foremost forum for showcasing and discussing the latest advances in ionic liquids. However, we, and others, resisted the temptation to produce proceedings volumes. Although having a certain value as a time capsule, such volumes date quickly, and individual chapters are poorly cited (as they usually appear around the same time in the primary journals). Nevertheless, taken together, the COIL speakers have been a remarkable group of chemists, chemical engineers, biochemists, and biologists. Surely such a talented assembly of scientists could make a valuable contribution, en masse, to the published literature. And so this volume, Ionic Liquids UnCOILed, slowly emerged from our collective mind: “UnCOILed” because, although every principal author has presented their work as COIL lectures, the chapter content in this book has never been presented there. We wrote to each of our selected authors (and, amazingly, only one turned us down!), and set them a difficult challenge. The letter we sent out included the following text: “The concept is to select the key speakers from COIL-1, COIL-2 and COIL-3 and invite them to write critical reviews on specific areas of ionic liquid chemistry. The area we have selected for you is […]. It is important to emphasise that these are meant to be critical reviews. We are not looking for comprehensive coverage, but insight, appreciation and prospect. We want the type of review which can be read to give a sense of importance and scope of the area, highlighting this by the best published work and looking for the direction in which the field is moving. We would also like the problems with the area highlighting, for example, poor experimental technique, poor selection of liquids, and variability of data. We hope you would like to be involved in this project, as we believe these books will define the field for the next few years.” Indeed, we felt rather like Division Seven, contacting the Impossible Missions Force (in the original, more cerebral, TV series, not the recent films!), “Your mission […] should you decide to accept it . . .” However, to the best of our knowledge, the emails did not “self-destruct in five seconds,” and the acceptance rate was beyond our best expectations. We also issued guidance as to which abbreviations to use, and so there is concordance between every chapter (unlike a recent book, which contained over 25 different abbreviations for a single ionic liquid!).

The quality and size of the reviews that we received meant that we had to revert to Wiley and ask permission to produce not one, but three books! Wiley generously agreed. Thus, this will be the first of three volumes. The following ones, at six monthly intervals, will be Ionic Liquids Further UnCOILed and Ionic Liquids Completely UnCOILed. All will contain overviews of the same critical nature.

We look forward to the response of our readership (we can be contacted at [email protected]). It is our view that, in the second decade of the 21st century, reviews that merely regurgitate a list of all papers on a topic, giving a few lines or a paragraph (often the abstract!) to each one, have had their day. Five minutes with an online search engine will provide that information. The value of a review lies in the expertise and insight of the reviewer—and their willingness to share it with the reader. It takes moral courage to say “the work of […] is irreproducible, or of poor quality, or that the conclusions are not valid”—but in a field expanding at the prestigious rate of ionic liquids, it is essential to have this honest feedback. Otherwise, errors are propagated. Papers still appear using hexafluorophosphate or tetrafluoroborate ionic liquids for synthetic or catalytic chemistry, and calculations on “ion pairs” are still being used to rationalise liquid state properties! We trust that this volume, containing 11 excellently perceptive reviews, will help guide and secure the future of ionic liquids.

NATALIA V. PLECHKOVAKENNETH R. SEDDON

ACKNOWLEDGEMENTS

This volume is a collaborative effort. We, the editors, have our names emblazoned on the cover, but the book would not exist in its present form without support from many people. First, we thank our authors for producing such splendid, critical chapters, and for their open responses to the reviewers’ comments and to editorial suggestions. We are also indebted to our team of expert reviewers, whose comments on the individual chapters were challenging and thought provoking, and to Ian Gibson for his input to the cover design. The backing from the team at Wiley, led by Dr. Arza Seidel, has been fully appreciated—it is always a joy to work with such a professional group of people. Finally, this book would never have been published without the unfailing, enthusiastic support from Deborah Poland, Sinead McCullough, and Maria Diamond, whose patience and endurance never cease to amaze us.

N.V.P.K.R.S.

CONTRIBUTORS

RIHAB AL SALMAN, Clausthal University of Technology, D-38678 Clausthal-Zellerfeld, Germany

MOHAMMAD AL ZOUBI, Clausthal University of Technology, D-38678 Clausthal-Zellerfeld, Germany

JARED L. ANDERSON, Department of Chemistry, The University of Toledo, Toledo, OH, USA

ROB ATKIN, Centre for Organic Electronics, Chemistry Building, The University of Newcastle, Callaghan, New South Wales 2308, Australia

NATALIA BORISENKO, Clausthal University of Technology, D-38678 Clausthal-Zellerfeld, Germany

TIMO CARSTENS, Clausthal University of Technology, D-38678 Clausthal-Zellerfeld, Germany

ANDRÉ B. DE HAAN, Eindhoven University of Technology/Dept. of Chemical Engineering and Chemistry Process Systems Engineering, P.O. Box 513, 5600 MB Eindhoven, The Netherlands

SHERIF ZEIN EL ABEDIN, Electrochemistry and Corrosion Laboratory, National Research Centre, Dokki, Cairo, Egypt

FRANK ENDRES, Clausthal University of Technology, D-38678 Clausthal-Zellerfeld, Germany

WERNER FREYLAND, Karlsruhe Institute of Technology, Kaiserstrasse 12, D-76128 Karlsruhe, Germany

CHRISTA M. GRAHAM, Department of Chemistry, The University of Toledo, Toledo, OH, USA

ROBERT HAYES, Centre for Organic Electronics, Chemistry Building, The University of Newcastle, Callaghan, New South Wales 2308, Australia

EKATERINA I. IZGORODINA, School of Chemistry, Monash University, Wellington Rd, Clayton, Victoria 3800, Australia

JUNKO KAGIMOTO, Department of Biotechnology, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588, Japan

PETER LICENCE, School of Chemistry, The University of Nottingham, NG7 2RD, UK

KEVIN R.J. LOVELOCK, School of Chemistry, The University of Nottingham, NG7 2RD, UK

WYTZE (G.W.) MEINDERSMA, Eindhoven University of Technology/Department of Chemical Engineering and Chemistry Process Systems Engineering, P.O. Box 513, 5600 MB Eindhoven, The Netherlands

HIROYUKI OHNO, Department of Biotechnology, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588, Japan

MARIJA PETKOVIC, Instituto de Tecnologia Química e Biológica, Universidade Nova de Lisboa, Av. da República, 2780-157, Oeiras, Portugal

JENNIFER M. PRINGLE, ARC Centre of Excellence for Electromaterials Science, Monash University, Wellington Road, Clayton, Victoria 3800, Australia

ALEXANDRA PROWALD, Clausthal University of Technology, D-38678 Clausthal-Zellerfeld, Germany

MARK B. SHIFLETT, DuPont Central Research and Development, Experimental Station, Wilmington, Delaware 19880, USA

CRISTINA SILVA PEREIRA, Instituto de Tecnologia Química e Biológica, Universidade Nova de Lisboa, Av. da República, 2780-157, Oeiras, Portugal, and Instituto de Biologia Experimental e Tecnológica (IBET), Apartado 12, 2781-901, Oeiras, Portugal

DEBORAH WAKEHAM, Centre for Organic Electronics, Chemistry Building, The University of Newcastle, Callaghan, NSW 2308, Australia

AKIMICHI YOKOZEKI, 32 Kingsford Lane, Spencerport, New York 14559, USA

ABBREVIATIONS

IONIC LIQUIDS

GNCS

guanidinium thiocyanate

[HI-AA]

hydrophobic derivatised amino acid

IL

ionic liquid

poly(RTILs)

polymerisable room temperature ionic liquids

[PSpy]

3

[PW]

[1-(3-sulfonic acid)propylpyridinium]

3

[PW

12

O

40

]·2H

2

O

CATIONS

[1-C

m

-3-C

n

im]

+

1,3-dialkylimidazolium

[C

n

mim]

+

1-alkyl-3-methylimidazolium

[Hmim]

+

1-methylimidazolium

[C

1

mim]

+

1,3-dimethylimidazolium

[C

2

mim]

+

1-ethyl-3-methylimidazolium

[C

3

mim]

+

1-propyl-3-methylimidazolium

[C

4

mim]

+

1-butyl-3-methylimidazolium

[C

5

mim]

+

1-pentyl-3-methylimidazolium

[C

6

mim]

+

1-hexyl-3-methylimidazolium

[C

7

mim]

+

1-heptyl-3-methylimidazolium

[C

8

mim]

+

1-octyl-3-methylimidazolium

[C

9

mim]

+

1-nonyl-3-methylimidazolium

[C

10

mim]

+

1-decyl-3-methylimidazolium

[C

11

mim]

+

1-undecyl-3-methylimidazolium

[C

12

mim]

+

1-dodecyl-3-methylimidazolium

[C

13

mim]

+

1-tridecyl-3-methylimidazolium

[C

14

mim]

+

1-tetradecyl-3-methylimidazolium

[C

15

mim]

+

1-pentadecyl-3-methylimidazolium

[C

16

mim]

+

1-hexadecyl-3-methylimidazolium

[C

17

mim]

+

1-heptadecyl-3-methylimidazolium

[C

18

mim]

+

1-octadecyl-3-methylimidazolium

[C

8

C

3

im]

+

1-octyl-3-propylimidazolium

[C

12

C

12

im]

+

1,3-bis(dodecyl)imidazolium

[C

4

dmim]

+

1-butyl-2,3-dimethylimidazolium

[C

4

C

1

mim]

+

1-butyl-2,3-dimethylimidazolium

[C

6

C

7O1

im]

+

1-hexyl-3-(heptyloxymethyl)imidazolium

[C

4

vim]

+

3-butyl-1-vinylimidazolium

[D

mvim

]

+

1,2-dimethyl-3-(4-vinylbenzyl)imidazolium

[(allyl)mim]

+

1-allyl-3-methylimidazolium

[P

n

mim]

+

polymerisable 1-methylimidazolium

[C

2

mmor]

+

1-ethyl-1-methylmorpholinium

[C

4

py]

+

1-butylpyridinium

[C

4

m

β

py]

+

1-butyl-3-methylpyridinium

[C

4

m

γ

py]

+

1-butyl-4-methylpyridinium

[C

4

mpyr]

+

1-butyl-1-methylpyrrolidinium

[C

2

C

6

pip]

+

1-ethyl-1-hexylpiperidinium

[C

8

quin]

+

1-octylquinolinium

[H

2

NC

2

H

4

py]

+

1-(1-aminoethyl)-pyridinium

[H

2

NC

3

H

6

mim]

+

1-(3-aminopropyl)-3-methylimidazolium

[Hnmp]

+

1-methyl-2-pyrrolidonium

[N

1 1 2 2OH

]

+

ethyl(2-hydroxyethyl)dimethylammonium

[N

1 1 1 4

]

+

trimethylbutylammonium

[N

4 4 4 4

]

+

tetrabutylammonium

[N

6 6 6 14

]

+

trihexyl(tetradecyl)ammonium

[P

2 2 2(1O1

)]

triethyl(methoxymethyl)phosphonium

[P

4 4 4 3a

]

+

(3-aminopropyl)tributylphosphonium

[P

6 6 6 14

]

+

trihexyl(tetradecyl)phosphonium

[S

2 2 2

]

+

triethylsulfonium

ANIONS

[Ala]

−

alaninate

[

β

Ala]

−

β

-alaninate

[Arg]

−

arginate

[Asn]

−

asparaginate

[Asp]

−

aspartate

[BBB]

−

bis[1,2-benzenediolato(2-)-

O,O

′]borate

[C

1

CO

2

]

−

ethanoate

[C

1

SO

4

]

−

methylsulfate

[CTf

3

]

−

tris{(trifluoromethyl)sulfonyl}methanide

[Cys]

−

cysteinate

[FAP]

−

tris(perfluoroalkyl)trifluorophosphate

[Gln]

−

glutaminate

[Glu]

−

glutamate

[Gly]

−

glycinate

[His]

−

histidinate

[Ile]

−

isoleucinate

[lac]

−

lactate

[Leu]

−

leucinate

[Lys]

−

lysinate

[Met]

−

methionate

[Nle]

−

norleucinate

[NPf

2

]

−

bis{(pentafluoroethyl)sulfonyl}amide

[NTf

2

]

−

bis{(trifluoromethyl)sulfonyl}amide

[O

2

CC

1

]

−

ethanoate

[O

3

SOC

2

]

−

ethylsulfate

[OMs]

−

methanesulfonate (mesylate)

[OTf]

−

trifluoromethanesulfonate

[OTs]

−

4-toluenesulfonate, [4-CH

3

C

6

H

4

SO

3

]

−

(tosylate)

[Phe]

−

phenylalaninate

[Pro]

−

prolinate

[Ser]

−

serinate

[Suc]

−

succinate

[Thr]

−

threoninate

[Trp]

−

tryphtophanate

[Tyr]

−

tyrosinate

[Val]

−

valinate

TECHNIQUES

AES

Auger electron spectroscopy

AFM

atomic force microscopy

ANN

associative neural network

ARXPS

angle resolved X-ray photoelectron spectroscopy

ATR-IR

attenuated total reflectance infrared spectroscopy

BPNN

back-propagation neural network

CCC

counter-current chromatography

CE

capillary electrophoresis

CEC

capillary electrochromatography

COSMO-RS

CO

nductorlike

S

creening

MO

del for Real Solvents

COSY

CO

rrelation

S

pectroscop

Y

CPCM

conductor-like polarisable continuum model

CPMD

Car–Parrinello molecular dynamics

DFT

density functional theory

DRS

direct recoil spectroscopy

DSC

differential scanning calorimetry

DSSC

dye-sensitised solar cell

ECSEM

electrochemical scanning electron microscopy

EC-XPS

electrochemical X-ray photoelectron spectroscopy

EFM

effective fragment potential method

EI

electron ionisation

EOF

electro-osmotic flow

EPSR

empirical potential structure refinement

ES

electrospray mass spectrometry

ESI–MS

electrospray ionisation mass spectrometry

EXAFS

extended X-ray absorption fine structure

FAB

fast atom bombardment

FMO

fragment molecular orbital method

GC

gas chromatography

GGA

generalized gradient approximations

GLC

gas–liquid chromatography

GSC

gas–solid chromatography

HM

heuristic method

HPLC

high performance liquid chromatography

HREELS

high resolution electron energy loss spectroscopy

IGC

inverse gas chromatography

IR

infrared spectroscopy

IRAS

infrared reflection absorption spectroscopy

IR-VIS SFG

infrared visible sum frequency generation

ISS

ion scattering spectroscopy

L-SIMS

liquid secondary ion mass spectrometry

MAES

metastable atom electron spectroscopy

MALDI

matrix-assisted laser desorption

MBSS

molecular beam surface scattering

MIES

metastable impact electron spectroscopy

MLR

multi-linear regression

MM

molecular mechanics

MS

mass spectrometry

NMR

nuclear magnetic resonance

NR

neutron reflectivity

PDA

photodiode array detection

PES

photoelectron spectroscopy

PPR

projection pursuit regression

QM

quantum mechanics

QSAR

quantitative structure–activity relationship

QSPR

quantitative structure–property relationship

RAIRS

reflection absorption infrared spectroscopy

RI

refractive index

RNN

recursive neural network

RP-HPLC

reverse phase-high performance liquid chromatography

SANS

small angle neutron scattering

SEM

scanning electron microscopy

SFA

surfaces forces apparatus

SFC

supercritical fluid chromatography

SFG

sum frequency generation

SFM

systematic fragmentation method

SIMS

secondary ion mass spectrometry

STM

scanning tunnelling microscopy

SVN

support vector network

TEM

tunnelling electron microscopy

TGA

thermogravimetric analysis

TLC

thin layer chromatography

TPD

temperature programmed desorption

UHV

ultra-high vacuum

UPLC

ultra-pressure liquid chromatography

UPS

ultraviolet photoelectron spectroscopy

UV

ultraviolet

UV-Vis

ultraviolet-visible

XPS

X-ray photoelectron spectroscopy

XRD

X-ray powder diffraction

XRR

X-ray reflectivity

MISCELLANEOUS

Å

1 Ångstrom = 10

−10

 m

ACS

American Chemical Society

ATPS

aqueous two-phase system

BE

binding energy

BILM

bulk ionic liquid membrane

b.pt.

boiling point

BSA

bovine serum albumin

BT

benzothiophene

calc.

calculated

CB

Cibacron Blue 3GA

CE

crown ether

CLM

charge lever momentum

CMC

critical micelle concentration

CMPO

octyl(phenyl)-

N,N

-diisobutylcarbamoylmethylphosphine oxide

COIL

Congress on Ionic Liquids

CPU

central processing unit

d

doublet (NMR)

D

°

298

bond energy at 298 K

2D

two-dimensional

3D

three-dimensional

DBT

dibenzothiophene

DC18C6

dicyclohexyl-18-crown-6

4,6-DMDBT

4,6-dimethyldibenzothiophene

DMF

dimethylmethanamide (dimethylformamide)

2DOM

two-dimensional ordered macroporous

3DOM

three-dimensional ordered macroporous

DOS

density of states

DPC

diphenylcarbonate

DRA

drag-reducing agent

DSSC

dye-sensitised solar cell

E

enrichment

EDC

extractive distillation column

EOR

enhanced oil recovery

EPA

Environmental Protection Agency

EPSR

empirical potential structure refinement

eq.

equivalent

FCC

fluid catalytic cracking

FFT

fast Fourier transform

FIB

focused ion beam

FSE

full-scale error

ft

foot

GDDI

generalised distributed data interface

HDS

hydrodesulfurisation

HEMA

2-(hydroxyethyl) methacrylate

HOMO

highest occupied molecular orbital

HOPG

highly oriented pyrolytic graphite

HV

high vacuum

IgG

immunoglobulin G

IPBE

ion pair binding energy

ITO

indium-tin oxide

IUPAC

International Union of Pure and Applied Chemistry

J

coupling constant (NMR)

LCST

lower critical separation temperature

LLE

liquid–liquid equilibria

LUMO

lowest unoccupied molecular orbital

m

multiplet (NMR)

M

molar concentration

MBI

1-methylbenzimidazole

MCH

methylcyclohexane

MD

molecular dynamics

MDEA

methyl diethanolamine; bis(2-hydroxyethyl)methylamine

MEA

monoethanolamine; 2-aminoethanol

MFC

minimal fungicidal concentrations

MIC

minimal inhibitory concentrations

MNDO

modified neglect of differential overlap

m.pt.

melting point

3-MT

3-methylthiophene

MW

molecular weight

m/z

mass-to-charge ratio

NBB

1-butylbenzimidazole

NCA

N

-carboxyamino acid anhydride

NES

New Entrepreneur Scholarship

NFM

N

-formylmorpholine

NIP

neutral ion pair

NIT

neutral ion triplet

NMP

N

-methylpyrrolidone

NOE

nuclear Overhauser effect

NRTL

non-random two liquid

ocp

open circuit potential

p

pressure

PDMS

polydimethoxysilane

PEDOT

poly(3,4-ethylenedioxythiophene)

PEG

poly(ethyleneglycol)

PEN

poly(ethylene-2,6-naphthalene decarboxylate)

PES

polyethersulfone

pH

−log

10

([H

+

]); a measure of the acidity of a solution

p

K

b

−log

10

(

K

b

)

PPDD

polypyridylpendant poly(amidoamine) dendritic derivative

PS

polystyrene

psi

1 pound per square inch = 6894.75729 Pa

PTC

phase transfer catalyst

PTFE

poly(tetrafluoroethylene)

PTx

pressure–temperature–composition

r

bond length

RDC

rotating disc contactor

REACH

Registration, Evaluation, Authorisation and restriction of CHemical substances

RMSD

root-mean-square deviation

RT

room temperature

s

singlet (NMR)

S

entropy

scCO

2

supercritical carbon dioxide

SDS

sodium dodecyl sulfate

S/F

solvent-to-feed ratio

SILM

supported ionic liquid membrane

SLM

supported liquid membranes

t

triplet (NMR)

TBP

4-(

t

-butyl)pyridine

TCEP

1,2,3-tris(2-cyanoethoxy)propane

TEGDA

tetra(ethylene glycol) diacrylate

TMB

trimethylborate

TOF

time-of-flight

UCST

upper critical solution temperature

UHV

ultrahigh vacuum

UV

ultraviolet

VLE

vapour–liquid equilibria

VLLE

vapour–liquid–liquid equilibria

VOCs

volatile organic compounds

v/v

volume for volume

w/w

weight for weight

wt%

weight per cent

γ

surface tension

δ

chemical shift in NMR

X

molar fraction

1 

Electrodeposition from Ionic Liquids: Interface Processes, Ion Effects, and Macroporous Structures

FRANK ENDRES, NATALIA BORISENKO, RIHAB AL SALMAN, MOHAMMAD AL ZOUBI, ALEXANDRA PROWALD, and TIMO CARSTENS

Clausthal University of Technology, Clausthal-Zellerfeld, Germany

SHERIF ZEIN EL ABEDIN

Electrochemistry and Corrosion Laboratory, National Research Centre, Dokki, Cairo, Egypt

ABSTRACTIn this chapter, we discuss the prospects and challenges of ionic liquids for interfacial electrochemistry and electrodeposition processes. In contrast to aqueous or organic solutions, ionic liquids form surprisingly strongly adhering solvation layers that vary with the applied electrode potential and that alter the tunnelling conditions in a scanning tunnelling microscopy (STM) experiment. Different cation–anion combinations can have an impact on the fundamental electrochemical processes, and the purity of ionic liquids is a key factor in interfacial electrochemistry. It is also shown that ionic liquids have a high potential in the making of three-dimensional ordered macroporous structures of semiconductors.

1.1 INTRODUCTION

Until about the year 2000, most papers dealing with electrochemistry or electrodeposition in or from ionic liquids used systems based on aluminium(III) chloride and 1,3-dialkylimidazolium ions, which were first reported in 1982 [1]. Although Walden reported in his paper from 1914 [2] on liquids that we often call today “air and water stable ionic liquids,” a community of about 10–20 groups worldwide investigated AlCl3-based liquids from 1948 onwards, which can only be handled under the conditions of an inert-gas dry box. One can speculate about the reasons, but one explanation might be that these liquids are (still) relatively easy to produce: mix carefully water-free aluminium(III) chloride with a well-dried organic halide (e.g., 1-butyl-3-methylimidazolium chloride) in a glove box and, depending on the ratio of the components, a Lewis acidic or a Lewis basic liquid is obtained. As aluminium(III) chloride adsorbs and reacts with water, even under the conditions of a dry box, some ageing takes place, which produces less defined oxochloroaluminates(III) by hydrolysis. As aluminium can be easily electrodeposited from these liquids, a common purification method is to perform a refining electrolysis with an aluminium anode and a steel cathode, leading to clear and well-defined electrolytes. A major review on these liquids was written by Hussey [3], and his article well summarises the prospects of these liquids, which were mainly used as electrolytes for the electrodeposition of aluminium and its alloys, and a few other metals [4]. One can say that, in 2000, there seemed to be no more surprises with these liquids and that electrochemical processes seemed to be well understood, except for, maybe, a few unusual observations (mainly reported in meetings), for example, that aluminium deposition is rather problematic if tetraalkylammonium ions are used instead of imidazolium ions. Furthermore, there was practically no understanding of the interfacial electrochemical processes. As these liquids can only be handled under the conditions of a dry box, scanning tunnelling or atomic force microscopy experiments (STM/AFM), which are well suited for such purposes, were extremely demanding. Nevertheless, one of the authors of this chapter (FE) and Freyland showed in a pioneering, but hardly cited, paper [5] that STM experiments can be performed in aluminium(III) chloride-based ionic liquids and that the surface of highly oriented pyrolytic graphite (HOPG) can be resolved atomically. In subsequent papers, it was shown that the surface and the initial deposition steps on Au(111) as a well-defined model surface can be probed in these liquids. Underpotential phenomena that can lead to alloying, sub-monolayer island deposition, and Moiré patterns [6–9] were found. Later results showed that the Au(111) surface seemed to be resolved atomically in a limited potential régime [10]. Although the latter result was a good step forward, the question remained as to why atomic resolution is much more difficult in ionic liquids than in aqueous solutions, where even atomic processes in real time were demonstrated [11].