Electrodeposition from Ionic Liquids E-Book

• Herausgeber: Wiley-VCH Verlag GmbH & Co. KGaA
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 1053

Veröffentlichungsjahr: 2017

Beschreibung

Edited by distinguished experts in this expanding field and with specialist contributions, this overview is the first of its kind to focus on electrodeposition from ionic liquids.
This second edition has been completely revised and updated with approximately 20% new content and has been expanded by five chapters to cover the following topics:
-Bulk and Interface Theory
-Nanoscale Imaging including AFM, In situ STM and UHV-STM
-Impedance Spectroscopy
-Process Scale-up including Brighteners
-Speciation and Redox Properties.
The result is essential reading for electrochemists, materials scientists, chemists in industry, physical chemists, chemical engineers, inorganic and organic chemists.

Leseprobe

Table of Contents

Cover

Title Page

Copyright

List of Contributors

Abbreviations

Chapter 1: Why Use Ionic Liquids for Electrodeposition?

1.1 Nonaqueous Solutions

1.2 Ionic Fluids

1.3 What Is an Ionic Liquid?

1.4 Technological Potential of Ionic Liquids

1.5 Conclusions

References

Chapter 2: Synthesis of Ionic Liquids

2.1 Nanostructured Metals and Alloys Deposited from Ionic Liquids

References

2.2 Air- and Water-Stable Ionic Liquids

References

2.3 Eutectic-Based Ionic Liquids

References

Chapter 3: Physical Properties of Ionic Liquids for Electrochemical Applications

3.1 Introduction

3.2 Thermal Properties

3.3 Viscosity

3.4 Density

3.5 Refractive Index

3.6 Polarity

3.7 Solubility of Metal Salts

3.8 Electrochemical Properties

3.9 Conclusion and Future Prospects

Acknowledgments

References

Chapter 4: Electrodeposition of Metals

4.1 Electrodeposition in AlCl

3

-Based Ionic Liquids

References

4.2 Electrodeposition of Refractory Metals from Ionic Liquids

References

4.3 Deposition of Metals from Nonchloroaluminate Eutectic Mixtures

References

4.4 Troublesome Aspects

References

4.5 Complexation and Redox Behavior of Metal Ions in Ionic Liquids

References

Chapter 5: Electrodeposition of Alloys

5.1 Introduction

5.2 Electrodeposition of Al-Containing Alloys from Chloroaluminate Ionic Liquids

5.3 Electrodeposition of Zn-Containing Alloys from Chlorozincate Ionic Liquids

5.4 Fabrication of a Porous Metal Surface by Electrochemical Alloying and Dealloying

5.5 Nb–Sn

5.6 Air- and Water-Stable Ionic Liquids

5.7 Deep Eutectic Solvents

5.8 Summary

References

Chapter 6: Electrodeposition of Semiconductors from Ionic Liquids

6.1 Introduction

6.2 Group IV Semiconductors

6.3 II–VI Compound Semiconductors

6.4 III–V Compound Semiconductors

6.5 Other Compound Semiconductors

6.6 Conclusions

References

Chapter 7: Conducting Polymers

7.1 Introduction

7.2 Electropolymerization – General Experimental Procedures

7.3 Synthesis of Conducting Polymers in Chloroaluminate ILs

7.4 Synthesis of Conducting Polymers in Air- and Water-Stable ILs

7.5 Characterization

7.6 Conclusions and Outlook

References

Chapter 8: Nanostructured Materials

8.1 Nanostructured Metals and Alloys Deposited from Ionic Liquids

References

8.2 Electrodeposition of Ordered Macroporous Materials from Ionic Liquids

References

8.3 Electrodeposition of Nanowires from Ionic Liquids

References

8.4 Electrochemical Synthesis of Nanowire Electrodes for Lithium Batteries

References

Chapter 9: Ionic Liquid–Solid Interfaces

9.1 Introduction

9.2 IL–Au(1 1 1) Interface

9.3 IL–HOPG Interface

9.4 Influence of Solutes on the IL–Electrode Interfacial Structure

9.5 Thin Films of Ionic Liquids in Ultrahigh Vacuum (UHV)

9.6 Outlook

References

Chapter 10: Plasma Electrochemistry with Ionic Liquids

10.1 Introduction

10.2 Concepts and Principles

10.3 Early Studies

10.4 The Stability of Ionic Liquids in Plasma Experiments

10.5 Plasma Electrochemical Metal Deposition in Ionic Liquids

10.6 Conclusions and Outlook

Acknowledgments

References

Chapter 11: Impedance Spectroscopy

11.1 Introduction

11.2 Measurement: Basics and Pitfalls

11.3 Analysis of Experimental Data

11.4 Application: IL Interfaces at Metal Electrodes

References

Chapter 12: Technical Aspects

12.1 Metal Dissolution Processes

References

12.2 Reference Electrodes for Use in Room-Temperature Ionic Liquids

References

12.3 Process Scale-Up

References

12.4 Toward Regeneration and Reuse of Ionic Liquids in Electroplating

References

12.5 Impurities

A.1 Protocol for the Deposition of Zinc from a Type III Ionic Liquid

A.2 Electroplating Experiment

References

Chapter 13: Plating Protocols

13.1 Electrodeposition of Al from [C

2

mim]Cl/AlCl

3

13.2 Electrodeposition of Al from 1-Butyl-3-methylimidazoliumchloride–AlCl

3

–Toluene

13.3 Electrodeposition of Al from [C

2

mim] NTf

2

/AlCl

3

13.4 Electrodeposition of Al from [C

4

mpyr]NTf

2

/AlCl

3

13.5 Electrodeposition of Li from [C

4

mpyr]NTf

2

/LiNTf

2

13.6 Electrodeposition of Ta from [C

4

mpyr]NTf

2

13.7 Electrodeposition of Zinc Coatings from a Choline Chloride: Ethylene-Glycol-Based Deep Eutectic Solvent

13.8 Electrodeposition of Nickel Coatings from a Choline Chloride: Ethylene-Glycol-Based Deep Eutectic Solvent

References

Chapter 14: Future Directions and Challenges

14.1 Impurities

14.2 Counter Electrodes/Compartments

14.3 Ionic Liquids for Reactive (Nano)materials

14.4 Nanomaterials/Nanoparticles

14.5 Cation/Anion Effects

14.6 Polymers for Batteries and Solar Cells

14.7 Variable-Temperature Studies

14.8 Intrinsic Process Safety

14.9 Economics (Price, Recycling)

14.10 Fundamental Knowledge Gaps

Index

End User License Agreement

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Guide

Cover

Table of Contents

Begin Reading

List of Illustrations

Chapter 1: Why Use Ionic Liquids for Electrodeposition?

Figure 1.1 Publications on the topic of electrodeposition using ionic liquids, 1991 to mid-2015 (Web of Science).

Figure 1.2 Summary of the elements deposited as single metals or alloys.

Chapter 2: Synthesis of Ionic Liquids

Scheme 2.1.1 General synthesis route to haloaluminate-based ionic liquids.

Figure 2.1.1 Examples of cations commonly used for the synthesis of ionic liquids.

Scheme 2.1.2 Quaternization reaction of 1-alkylimidazoles.

Scheme 2.1.3 Reaction between [EMIM]Cl and AlCl

3

.

Scheme 2.1.4 Autosolvolysis of AlCl

4

melts.

Scheme 2.2.1 General synthetic route to producing air- and moisture-stable ionic liquids.

Figure 2.2.1 Structure, full name, and abbreviations for the anions discussed in this section.

Figure 2.2.2 A comparison of the hydrolytic stability of four 1-hexyl-3-methylimidazolium ionic liquids [HMIM]X ionic liquids. To 25 g of each ionic liquid, 7.1 mol% water was added. These solutions were heated to 60 °C and the fluoride content measured once an hour for 8 hours. All measurements were performed at Merck KGaA, Darmstadt, Germany.

Figure 2.3.1 Schematic representation of a eutectic point on a two-component phase diagram.

Figure 2.3.2 Schematic representation of the complexation occurring when a Lewis acid or a Brønsted acid interacts with a quaternary ammonium salt.

Scheme 2.3.1 Example syntheses of metal oxide-based ionic liquids.

Chapter 3: Physical Properties of Ionic Liquids for Electrochemical Applications

Figure 3.1 Phase diagram for [C

n

mim]BF

4

showing the melting (), glass (), and clearing () transitions measured by differential scanning calorimetry.

Figure 3.2 Relation between thermal decomposition temperatures (

T

d

) of [C

n

mim]-type ILs and alkyl chain length (

n

). Anion species are Cl

−

: (), I

−

: (), : (), : () and [Tf

2

N]

−

: ().

Scheme 3.1 Pyrolysis mechanism of ILs containing halide anions.

Figure 3.3 Plot of refractive indices (

n

) versus density (ρ) for a series of ILs.

Figure 3.4 Solvatochromic probe molecules.

Figure 3.5 ILs containing multivalent anion.

Figure 3.6 Structure of zwitterionic salt for selective ion-conductive materials.

Chapter 4: Electrodeposition of Metals

Figure 4.1.1 Simplified electrochemical windows of 1-butyl-pyridinium chloride and 1-ethyl-3-methyl-imidazolium chloride.

Figure 4.1.2 Cathodic scan cyclic voltammograms of near-Lewis-neutral and LiCl-buffered [EMIM]Cl/AlCl

3

ionic liquids at a W working electrode. Scan rate: 100 mV s

−1

. (a) Negative scan limit: −2.2 V; (b) negative scan limit: −2.7 V.

Figure 4.1.3 Cyclic voltammogram of neutral buffered, unprotonated melt at tungsten (a) and 303 stainless steel (b).

Figure 4.1.4 Cyclic voltammogram at tungsten of a neutral buffered, ionic liquid protonated to a partial pressure of 6.1 Torr HCl.

Figure 4.1.5 XRD pattern of nanocrystalline Al with a grain size of 12 ± 1nm.

Figure 4.1.6 Size distribution of nanocrystalline Al TEM image.

Chapter 5: Electrodeposition of Alloys

Figure 5.1 Plan-view SEM images of silver wire samples that have been electrodeposited with 12.73 C cm

−2

of zinc followed by dealloying at 0.6 V. The amounts (in C cm

−2

) of the zinc that were dealloyed are as follows: (a) 1.59, (b) 4.77, (c) 9.55, and (d) 12.73 C cm

−2

. The temperature was 150 °C [43] and the scale bar in the SEM images is 2 μm. (Yeh (2006) [43]. Reproduced with permission of American Chemical Society.)

Figure 5.2 Staircase cyclic voltammograms of (......) 0.3 M Zn(II), (----) 0.2 M Mn(II), and (——) the mixture of 0.16 M Zn(II) + 0.1 M Mn(II) recorded at W electrode in [TBMA]Tf

2

N ionic liquid. Temperature, 80 °C. Scan rate, 50 mV s

−1

[53]. (Chen (2007) [53]. Reproduced with permission of Elsevier.)

Figure 5.3 A comparison of two cyclic voltammograms of 0.1 M FeCl

2

/[Py

1,4

]TfO and (0.1 M FeCl

2

+ 2.75 M AlCl

3

)/[Py

1,4

]TfO at 100 °C on copper at two different switching potentials. Scan rate, 10 mV s

−1

. The CV of neat [Py

1,4

]TfO on copper at 100 °C is shown in the inset [58]. (Giridhar (2014) [58] http://pubs.rsc.org/en/content/articlelanding/2014/cp/c4cp00613e#!divAbstract. Used under CC-BY-3.0 https://creativecommons.org/licenses/by/3.0/.)

Figure 5.4 Voltammograms (scan rate, 20 mV s

−1

) for a Pt microelectrode (0.5 mm diameter) immersed in (a) 1 : 2 ChCl:EG, and (b) 1 : 2 ChCl:U DES containing 0.05 M SnCl

2

and 0.5 M ZnCl

2

[67]. (Abbott (2007) [67]. Reproduced with permission of Elsevier.)

Chapter 6: Electrodeposition of Semiconductors from Ionic Liquids

Figure 6.1

In situ

STM images of Au(111) in (a) 0.1 M SiCl

4

/[C

4

mPyr][N(Tf)

2

] at –1.6 V and (b) 0.1 M SiCl

4

/[C

4

mPyr][FAP] at –0.6 V.

In situ

I/U tunneling spectroscopy reveals a band gap of 1.1 eV (insets) indicating that semiconducting Si has been deposited in both solutions.

Figure 6.2 XRD pattern of crystalline Ga-doped Ge deposited electrochemically on Cu from [C

2

mim][N(Tf)

2

] at room temperature.

Figure 6.3 SEM images of free-standing Ge nanowires (a), nanotubes with 220 nm in diameter (b), and nanotubes with 400 nm in diameter (c) electrodeposited from 0.1 M GeCl

4

/[C

2

mim][N(Tf)

2

].

Figure 6.4

In situ

AFM images of electroless deposition of Sb on Ga from 0.25 M SbCl

3

/[C

4

mPyr][N(Tf)

2

].

Chapter 7: Conducting Polymers

Figure 7.1 The chemical structure of common conducting polymers, in their undoped, neutral form.

Figure 7.2 The redox cycling of poly(pyrrole) involving intercalation and expulsion of (a) the anion, or (b) the cation, from the electrolyte to effect charge balance.

Figure 7.3 The polymerization mechanism for heterocyclic polymers.

Figure 7.4 The cations and anions utilized for the electrochemical synthesis of conducting polymers in ILs, and the abbreviations used herein.

Figure 7.5 Poly(pyrrole) films grown in [C

4

mpyr][NTf

2

] (a), [C

2

mim][NTf

2

] (b), and PC/Bu

4

N PF

6

(c), by constant potential onto Pt.

Figure 7.6 Growth of poly(pyrrole) in (a) air-equilibrated [C

4

mim][PF

6

], (b) [C

4

mim][PF

6

] after N

2(g)

purging, and (c) deoxygenated 0.25 M Bu

4

N PF

6

in PC, 100 mV s

−1

, 30 cycles.

Figure 7.7 Poly(pyrrole) grown along the surface of [C

2

mim][NTf

2

] at (a) constant potential, (b) with a circular auxiliary electrode, (c) using voltage pulses.

Figure 7.8 Cyclic voltammograms of thiophene polymerization (0.2 M, 50 mV s

−1

) onto a Pt working electrode; (a) growth and (b) postgrowth in [C

2

mim][NTf

2

], (c) growth and (d) postgrowth in [C

4

mpyr][NTf

2

], versus a Ag pseudo reference electrode. Arrows indicate the peak development with successive scans.

Figure 7.9 Cyclic voltammograms of bithiophene polymerization (0.1 M, 50 mV s

−1

) (a) growth and (b) postgrowth in [C

2

mim][NTf

2

], (c) growth and (d) postgrowth in [C

4

mpyr][NTf

2

], versus a Ag pseudo reference electrode. Arrows indicate the peak development with successive scans.

Figure 7.10 Cyclic voltammograms of terthiophene polymerization (0.01 M, 50 mV s

−1

) (a) growth and (b) postgrowth in [C

2

mim][NTf

2

], (c) growth and (d) postgrowth in [C

4

mpyr][NTf

2

], versus a Ag pseudo reference electrode.

Figure 7.11 Cyclic voltammograms of PEDOT (0.1 M, 20 cycles, every third shown, 100 mV s

−1

). (a) Film I growth in acetonitrile/Bu

4

N ClO

4

. (b) Postgrowth of films I and II in acetonitrile/Bu

4

N ClO

4

. (c) Film II – growth in [C

2

mim][NTf

2

] and (d) postgrowth of films I and II in [C

2

mim][NTf

2

], versus an Ag pseudo reference electrode.

Figure 7.12 Current–time responses to potential step from 0 to 1.4 V for the electropolymerization of 0.1 M EDOT onto ITO electrodes in different media: (a) 0.1 M Bu

4

N ClO

4

in acetonitrile, (b) [C

4

mpyr][NTf

2

], (c) 0.1 M LiNTf

2

in acetonitrile, and (d) [C

2

mim][NTf

2

].

Figure 7.13 High resolution SEM images of TiO

2

-containing PPP nanowires after dissolution of the polycarbonate membrane.

Figure 7.14 SEMs of poly(thiophene) films grown from [C

2

mim][NTf

2

] (a–c) and [C

4

mpyr][NTf

2

] (d–f), viewed from above (a, d and b, e) and edge view (c, f).

Figure 7.15 SEM images of reduced PEDOT films on ITO, prepared by cyclic voltammetry (20 cycles, 100 mV s

−1

) from (a) 0.1 M LiNTf

2

in acetonitrile, (b) [C

4

mpyr][NTf

2

], (c) [C

2

mim][NTf

2

], and (d) 0.1 M Bu

4

N ClO

4

in acetonitrile.

Figure 7.16 Examples of Raman spectra of (a) poly(pyrrole) and (b) poly(terthiophene), from [C

2

mim][NTf

2

].

Figure 7.17 Example of the deconvolution of XPS spectra for poly(pyrrole) containing [NTf

2

] anions and [C

2

mim] cations.

Figure 7.18 UV-vis spectra of PEDOT films (a) deposited in [C

2

mim][NTf

2

], oxidized 20 min at 0.8 V, and reduced 20 min at −1 V in the IL, (b) grown in [C

2

mim][NTf

2

], oxidized 20 min at 0.8 V, and reduced 20 min at −1 V in acetonitrile/0.1 M Bu

4

N ClO

4

solution (c) spectroelectrochemistry of PEDOT in 0.1 M LiNTf

2

in acetonitrile after deposition from [C

4

mpyr][NTf

2

] from −1 to 0.9 V.

Figure 7.19 (a)

31

P, (b)

19

F, and (c)

13

C NMR spectra of polypyrrole grown at constant potential in [P

6,6,6,14

][NTf

2

].

Chapter 8: Nanostructured Materials

Figure 8.1.1 The crystallite size dependence of the pulsed current density for gold deposits deposited from a commercial sulfite bath without any additives [29].

Figure 8.1.2 The effect of the time on the nanostructure of gold deposits. An average current density of was used for all experiments [29].

Figure 8.1.3 The activity of different grain refiners (butanediamine, ammonium ethylenediamine tetraacetic acid, benzosulfimide) on the nanostructure of gold deposits [29].

Figure 8.1.4 The influence of the concentration of the electrolyte on the alloy composition [29].

Figure 8.1.5 The influence of the temperature (left axis) and the pulse current density (right axis) on the alloy composition of FeNi alloys [29].

Figure 8.1.6 The influence of the benzoic acid concentration on the crystallite size of aluminum deposits [74].

Figure 8.1.7 Cyclic voltammograms for aluminum deposition with increasing amounts of additive (benzoic acid) [74].

Figure 8.1.8 Temperature dependence of the crystallite size for Al samples prepared from additive-containing electrolyte [74].

Figure 8.1.9 X-ray diffraction pattern of an AlMn alloy prepared from a Lewis acid electrolyte [74].

Figure 8.1.10 (a) A biphasic mixture of the ionic liquid 1-butyl-1-methyl pyrrolidinium bis(trifluoromethylsulfonyl)imide containing at room temperature. (b) The biphasic mixture becomes monophasic at 80 °C [89].

Figure 8.1.11 Cyclic voltammogram recorded at the Au(111) substrate in the ionic liquid 1-butyl-1-methyl pyrrolidinium bis(trifluoromethylsulfonyl)imide containing (from the upper phase of the mixture) at room temperature. The scan rate was [89].

Figure 8.1.12 SEM micrographs of electrodeposited Al on gold formed after potentiostatic polarization for 2 h in the upper phase of the mixture : (a) at room temperature, ; (b) at 100 °C, . (c) EDAX profile for the area shown in the SEM micrograph (a) [89].

Figure 8.1.13 XRD patterns of an electrodeposited Al layer obtained potentiostatically at for 2 h in the upper phase of the mixture at 100 °C on a glassy carbon substrate. Inset: FWHM of Al(111) peak of XRD patterns [89].

Figure 8.1.14 SEM micrographs of electrodeposited Al films on gold formed in the upper phase of the mixture after potentiostatic polarization for 2 h at (a) room temperature (, corresponding ); (b) 50 °C (, corresponding ); (c) 75 °C (, corresponding ); and (d) 100 °C (, corresponding ) [91].

Figure 8.1.15 SEM micrographs of electrodeposited Al films on gold formed after potentiostatic polarization for 1 h in the upper phase of the mixture at (a) 25 °C (, corresponding ); (b) 50 °C (, corresponding ); (c) 75 °C (, corresponding ); and (d) 100 °C (, corresponding ) [91].

Figure 8.1.16 Cyclic voltammogram of the ionic liquid saturated with on gold at room temperature. Scan rate [93].

Figure 8.1.17 (a) SEM micrograph of nanocrystalline copper obtained potentiostatically on Au in the ionic liquid saturated with at a constant potential for 2 h at room temperature. (b) EDX profile of the area shown in the SEM micrograph [93].

Figure 8.2.1 (a) SEM image of a PS colloidal crystal. (b) SEM image of a 3DOM structure of nickel by electrodeposition.

Figure 8.2.2 High-resolution SEM images of 3DOM Ge obtained after applying a constant potential of −1.9 V (vs Ag quasi-reference electrode) for 3 h at room temperature. Scale bars: (a) 500 nm, (b) 2 µm.

Figure 8.2.3 Optical photographs of the deposited Ge photonic crystal (pore size about 370 nm) on the ITO glass substrate showing a color change when the angle of incident white light is changed. The deposit was obtained after potentiostatic polarization at −2 V (vs Ag quasi-reference electrode) for 30 min in [C

2

mim][NTf

2

].

Figure 8.2.4 Anode performance in half-cells: (a) discharge–charge curves of 3DOM Ge between 0 and 2 V at 0.2C; (b) cycling behaviors of the 3DOM Ge and dense Ge electrodes; (c) cycling performances of the 3DOM Ge and dense Ge electrodes under different rates; (d) capacity vs. cycle number and discharge/charge rate.

Figure 8.2.5 SEM images of 3DOM silicon from PS templates with different diameters: (a) with 235 nm particles, (b) with 455 nm particles, and (c) with 515 nm particles. The insets show the 2D fast Fourier transform (FFT) analysis of the samples.

Figure 8.2.6 SEM image of PS template assembled from 500-nm-diameter PS spheres on ITO substrate (a). SEM images of 2D macroporous thin film electrodeposited (b) at room temperature and (c) at 90 °C.

Figure 8.2.7 Illustration of the formation of the two kinds of 2D architectures. (a) PS template obtained by self-assembly; (b) PS template obtained after annealing at elevated temperature; (c, d) infiltration of the template by electrodeposition for 15 min; (e, f) removal of the PS spheres by DMF to obtain a 2D film.

Figure 8.2.8 Optical photographs of deposited 2D ordered structure (PS sphere size 500 nm, SiCl

4

:GeCl

4

= 1 : 1) on ITO substrate showing a color variation with changing the angle of incident white light.

Figure 8.2.9 SEM image of Ga macroporous structure obtained after the dissolution of the PS template. Deposition potential: −1.4 V, deposition time: 1 h.

Figure 8.2.10 Cyclic voltammogram for the Cu/polystyrene template electrode in [C

2

mim]Cl/AlCl

3

at a scan rate of 10 mV s

−1

.

Figure 8.2.11 (a, b) SEM image of macroporous PEDOT on gold after removal of the PS template.

Figure 8.2.12 Photographs of the macroporous PEDOT film deposited on gold. The PEDOT film turns green, red, blue, and orange with slight change of the angle of the incident visible light.

Figure 8.2.13 Schematic illustration of 3DOM bilayer films electrodeposited from ionic liquids.

Chapter 9: Ionic Liquid–Solid Interfaces

Figure 9.1 Typical normal forces versus apparent separation data for [EMIm] FAP (a–c), [BMIm] FAP (d–f), [HMIm] FAP (g–i), and [BMIm] I (j–l) at Au(1 1 1) as a function of potential. For the chemical structures of the ILs: carbon atoms are shaded gray, nitrogen are blue, hydrogen are white, fluorine are yellow, phosphorous are pink, and iodide are red.

Figure 9.2

In situ

STM images of the Au(1 1 1) surface at the OCP and at –1.0 V in [Py

1,4

] FAP (a, d), [EMIm] FAP (b, e), and [HMIm] FAP (c, f).

Figure 9.3

In situ

STM images of the Au(1 1 1) surface at the OCP and at –1.0 V in [Py

1,4

] Tf

2

N (a, d), [EMIm] Tf

2

N (b, e), and [OMIm] Tf

2

N (c, f).

Figure 9.4 Typical normal forces versus apparent separation data for [HMIm] FAP (a–c), [EMIm] FAP (d–f), [EMIm] Tf

2

N (g–i), and [OMIm] Tf

2

N (j–l) at HOPG as a function of potential. For the chemical structures, carbon atoms are shaded gray; nitrogen are blue, hydrogen are white, fluorine are yellow, phosphorous are pink, sulfur are brown, and oxygen are red.

Figure 9.5 Normal force versus apparent separation (a–c) for [OMIm] Tf

2

N at –2.0 V as a function of time.

Figure 9.6

In situ

STM images of the Au(1 1 1) surface in [OMIm] Tf

2

N at different electrode potentials.

Figure 9.7 AM-AFM phase images of the pure [EMIm] TF

2

N Stern layer adsorbed to a graphite (HOPG) substrate. The slow scan direction of all images is down the images. Image sizes are all 15 nm × 15 nm. The interfacial data were collected at differing applied potentials and OCP (indicated in the figure). The OCP for the pure [EMIm] Tf

2

N system was 0.26 V versus Pt.

Figure 9.8 AM-AFM phase images of [EMIm] TF

2

N

+

0.1 wt% Li Tf

2

N and [EMIm] Tf

2

N

+

0.1 wt% [EMIm] Cl Stern layer adsorbed to a graphite (HOPG) substrate. The slow scan direction of all images is down the images. Image sizes are all 15 nm

×

15 nm. The interfacial data was collected at differing applied potentials and open-circuit potential (OCP) (indicated in the figure). The OCPs for the [EMIm] Tf

2

N

+

Li Tf

2

N 0.1 wt/wt% and [EMIm] Tf

2

N + [EMIm] Cl 0.1 wt/wt% systems were 0.30 V versus Pt and 0.42 V versus Pt, respectively. The slow scan direction of all images is down the images.

Figure 9.9

In situ

STM images of the Au(1 1 1) surface obtained in the pure [Py

1,4

] FAP (a, e), 0.1 M TaF

5

/[Py

1,4

] FAP (b, f), 0.1 M LiCl/[Py

1,4

] FAP (c, g), and 0.1 M SiCl

4

/[Py

1,4

] FAP (d, h) during cathodic polarization.

Figure 9.10 (a) XPS survey spectrum of [OMIM] Tf

2

N deposited on HOPG. (b) XPS detailed spectrum of the N1s core-level orbital.

Figure 9.11 XPS detailed spectra of the N1s core-level orbital of [Py

1,4

] Tf

2

N deposited on (a) a clean surface and (b) a Li precovered Cu surface.

Figure 9.12 UHV-STM images of [Py

1,4

] FAP deposited on Au(1 1 1): (a) at room temperature (298 K, 20 nm × 20 nm), (b) at reduced temperature (210 K, 10 nm × 10 nm).

Chapter 10: Plasma Electrochemistry with Ionic Liquids

Figure 10.1 Positive space charge layer at the interface between a plasma and (a) a dielectric, (b) a metallic, and (c) an electrolytic wall with floating potential φ

w

.

Figure 10.2 Different types of plasma reactors employing the use of an IL: (a) DC discharge with the IL as an integral part of a serial setup, (b) DC discharge with the IL as optional part of a parallel setup, (c) inductively coupled RF discharge with an electric circuit for electrochemical experiments independent from the plasma generating process.

Figure 10.3 Setup of the reproduced Gubkin experiment: silver is dissolved at the anode inside of the liquid electrolyte and reduced at the plasma–electrolyte interface; photograph of the laboratory experiment.

Figure 10.4 Experimental setups for different plasma (electro)chemical experiments: (a) DC setup of Klemenc, (b) setup for the recovery of metal from slags, and (c) vapor-phase electrolytic deposition setup of Ogumi

et al.

Figure 10.5 Decomposition pathways of 1,1-butylmethylpyrrolidinium according to Ref. [51].

Figure 10.6 Decomposition pathways of 1-butyl-3-methylimidazolium according to Ref. [51].

Figure 10.7 Decomposition pathways of 1-butyl-3-methylimidazolium via a biradical transition state.

Figure 10.8 Schematic experimental setup for the deposition of metal nanoparticles by plasma electrochemical reduction of a metal salt dissolved in an ionic liquid at room temperature.

Figure 10.9 DC discharge over [BMIM][TfO].

Figure 10.10 Plasma electrochemical deposition of silver nanoparticles at the free surface of [BMIM][TfO].

Figure 10.11 SEM image of the silver nanoparticles.

Figure 10.12 TEM image and size distribution of the silver nanoparticles.

Figure 10.13 Ar/H

2

(3 : 1) plasma burning over Cu(CF

3

SO

3

)

2

dissolved in [EMIM][TfO] with a brown cloud and black deposits. The distance amounts to only 4.5 cm; thus, the plasma consists mostly of dark space (Faraday space).

Figure 10.14 HRSEM picture of the obtained palladium nanoparticles.

Figure 10.15 HRTEM/SAED picture of the palladium nanoparticles. The letters in the SAED picture represent the lattice indices:

a =

111,

b =

200,

c =

220,

d =

311.

Chapter 11: Impedance Spectroscopy

Figure 11.1 (a) Phase shift between AC voltage and current. (b) Illustration of the impedance in a complex plane.

Figure 11.2 Impedance and capacitance spectrum of a serial

R

Bulk

C

DL

equivalent circuit (

R

Bulk

= 10 kΩ and

C

DL

= 5 μF) in the complex planes.

Figure 11.3 The Randles circuit. The serial bulk resistance of the electrolyte is ignored for clarity.

Figure 11.4 Impedance spectrum of the Randles circuit with

R

ct

= 500 Ω,

C

DL

= 5 μF, and σ = 300 Ω s

−0.5

.

Figure 11.5 Illustration of (a) two-electrode [5], (b) three-electrode [42], and (c) four-electrode [63] setups and their use for different kinds of electrochemical measurements.

Figure 11.6 Illustration of several cell designs used for EIS-based double-layer capacitance measurements. (a) A large cell with a Luggin-capillary-based RE; (b) a microcell used in the case of very small electrolyte volumes, which employs a vertical microreference electrode; and (c) a commercial cell for small electrolyte volumes with improved placement of the reference electrode (TSC surface, rhd instruments).

Figure 11.7 Visualization of the SSR as a function of the fit parameter vector

x

. There is a general tendency of fits to converge into local minima.

Figure 11.8 Example of initial parameter deduction directly from a measured impedance spectrum.

Figure 11.9 Illustration of the effect of proportional weighting on a fit. The inset shows a zoom into the high-frequency domain.

Figure 11.10 Lissajou plots of the system response to sinusoidal excitations. (a) Linear response with different phase angles. (b) Distortion caused by the presence of a 2nd harmonic response. (c) Distortion caused by the presence of a small noise signal with high frequency and small amplitude.

Figure 11.11 Differential capacitance versus electrode potential according to Korneyshev's mean-field lattice-gas model [95].

Figure 11.12 Capacitance spectrum of the [Pyrr

1,4

]FAP–Au(1 1 1) interface in the complex capacitance plane.

Figure 11.13 Differential capacitance of the fast and slow capacitive processes at the [Pyrr

1,4

]FAP|Au(1 1 1) interface, plotted versus the electrode potential

E

.

Figure 11.14 Differential capacitance of the fast capacitive process at the [EMIm]FAP|Au(1 1 1) interface, plotted versus the electrode potential

E

.

Figure 11.15

In situ

STM images of the Au(1 1 1) surface in contact with [Pyrr

1,4

]FAP at different electrode potentials.

Chapter 12: Technical Aspects

Figure 12.1.1 LSVs of (a) Co, (b) Ni, (c) Cu, and (d) Zn discs in Ethaline and BMIMCl at 70 °C with a sweep rate of 5 mV s.

Figure 12.1.2 Flow chart for the pretreatment of substrates before electrodeposition in ionic liquids.

Figure 12.1.3 AFM images of (a) aluminum and (b) copper etched for 20 s at 10 V in Ethaline (right side of image masked during experiment). (c) Depth profiles for Panels (a) and (b) are shown as dashed and solid lines, respectively.

Figure 12.2.1 Structures of all RTILs listed in Table 12.2.1.

Figure 12.2.2 Cyclic voltammograms for the oxidation of 5 mM ferrocene in on a platinum microelectrode (diameter ) at . Reference electrode was a Pt wire inserted into contained in a glass tube, separated by a Vycor frit. Preoxidation of the reference electrode took place for (a) 0 min, (b) 5 min, (c) 10 min, (d) 20 min, (e) 40 min, and (f) 20 min with 1 h “rest.”

Figure 12.2.3 Cyclic voltammograms for the oxidation of 5 mM ferrocene in on a platinum microelectrode (diameter ) at . Reference electrode was an Ag wire inserted into contained in a glass tube, separated by a Vycor frit. Preoxidation took place for (a) 0 min, (b) 5 min, (c) 10 min, and (d) 20 min.

Figure 12.2.4 Cyclic voltammograms for (a) the reduction of 12.5 mM benzoquinone (BQ) in on a platinum microelectrode (diameter ) at and (b) the oxidation of 20 mM

N

,

N

,

N′

,

N′

-tetramethylphenylenediamine (TMPD) in on a platinum electrode (diameter ) at .

Figure 12.2.5 Cyclic voltammetry of 20 mM TMPD in on a platinum electrode (diameter ) at in the presence of 0% and 100% hydrogen.

Figure 12.2.6 Outline of components of reference electrode, and the reference electrode inserted into a salt bridge compartment.

Figure 12.2.7 Cyclic voltammograms for the reduction of 84 mM AgTf in on a platinum microelectrode (diameter ) at scan rates of 200, 400, 700 mV s

−1

and 1, 2, 4, 7, 10 V s

−1

. The pseudo-reference electrode used was a silver wire. (b) Cyclic voltammetry for the reduction of 84 mM AgTf in on silver wire (diameter 0.5 mm) at with reference electrode as in Ref. [35].

Figure 12.3.1 Semi-industrial process-scale plant operating at OCAS in Ghent (a) with a 1 -m-long, 25-cm-diameter steel cathode (b) yielding a chromium morphology (c).

Figure 12.3.2 (a) Barrel plating pilot plant for coating screws with a Zn−Sn layer developed by Inasmet in San Sebastian. (b) Samples of Mg alloy coated with a Zn−Sn alloy by Protection des Metaux in Paris.

Figure 12.3.3 Immersion silver line at PW circuits (Leicester, UK) involving a nine tank systems, three of which contain ionic liquids.

Figure 12.3.4 Electropolishing bath (1300 L) operating at Anopol Ltd., (Birmingham, UK) based on an ethylene glycol:choline chloride eutectic.

Figure 12.3.5 A variety of pieces electropolished using a choline-based ionic liquid.

Figure 12.3.6 Recycling of ionic liquid (one ChCl:two ethylene glycol) used to electropolish stainless steel: (a) used liquid containing Fe, Cr, and Ni salts; (b) same as (a) with 1 equiv. v/v added water; (c) same as (b) after gravity filtration and subsequent removal of residual water by distillation.

Figure 12.4.1 Concept of sustainable use of process bath liquors in electroplating: recovery (rinsing and concentration), regeneration (concentration and purification), and reuse.

Figure 12.4.2 Samples of spent [BMP]Tf

2

N electrolyte (a) directly after electrodeposition of Al and (b) stirred at 75 °C in nitrogen atmosphere.

Figure 12.4.3 Samples after mixing with water, showing phase separation.

Figure 12.4.4 Recovered ionic liquid phase ([BMP]Tf

2

N) after regeneration.

Figure 12.4.5 Cyclic voltammograms of original and regenerated ionic liquid ([BMP]Tf

2

N). The potential was determined versus Pt as quasi-reference electrode. Scan rate 5 mV s

−1

.

Figure 12.5.1 Cyclic voltammogram of ultrapure [C

4

mpyr]TFSI on Au(111) with

v

= 10 mV s

−1

. The electrochemical window is 5.6 V. The reduction peaks C1–C3 are correlated with TFSI breakdown, which may be induced by ultralow amounts of water or other impurities.

Figure 12.5.2 The

in situ

STM picture evidences that the Au(111) surface near the open-circuit potential shows a worm-like surface pattern, likely due to interference between the gold surface and the [C

4

mpyr] cation.

Figure 12.5.3 The quality of the STM picture is reduced strongly in the potential regime of the reduction peaks C1–C3 in [C

4

mpyr]TFSI. The STM probes the breakdown of the TFSI, which may be induced by water and/or other impurities in the ultralow concentration regime.

Figure 12.5.4 (a) Cyclic voltammogram of [C

4

mpyr]TFSI (with low amounts of Li impurities) on Au(111): the processes C5 and C6 are typical for deposition in the UPD and OPD regimes, respectively. (b)

In situ

STM of Au(111) before C5: flat gold surface. (c)

In situ

STM of Au(111) between C5 and C6: obviously Li deposition has occurred.

Figure 12.5.5 Cyclic voltammograms (10 mV s

−1

) of [EMIM]TFSI (purified over silica) on Au(111), (a) 1st, (b) 7th, and (c) 15th cycles.

Figure 12.5.6

In situ

STM pictures of [EMIM]TFSI (purified over silica) on Au(111): obviously, there is a surface film adsorbed initially, which can be reduced to a nice terrace-like deposit.

Chapter 13: Plating Protocols

Figure 13.1 SEM image of an Al layer electroplated on mild steel at 20 mA cm

−2

.

Figure 13.2 The optical view of the cross section for an Al layer electroplated on mild steel at 20 mA cm

−2

.

Figure 13.3 The optical view of the cross section for an Al layer electroplated on mild steel at 20 mA cm

−2

with significant adherence improvement by

in situ

electrochemical etching.

Figure 13.4 An optical photo of deposits manufactured from the employed ionic liquid. The employed liquid can also be used to electroplate Al on an uneven surface or even a screw, as shown in Figure 13.4. The

in situ

etching leads to Al layers all showing satisfactory adhesive qualities.

Figure 13.5 Photos showing (a) the dull finish at 0.5 V and (b) the bright finish at 1.0 V.

Figure 13.6 SEM images of (a) the dull finish at 0.5 V and (b) the bright finish at 1.0 V.

Figure 13.7 (a) SEM image of an about 10 µm aluminum layer electrodeposited galvanostatically on a mild steel substrate at −5 mA cm

−2

. Inset: SEM image of higher magnification showing the excellence of the coating adhesion. (b) SEM image of the polished cross section of the deposited aluminum layer [2].

Figure 13.8 An optical photo of a deposited Al layer formed potentiostatically at −0.3 V (vs . Ae/Ae

3+

) in the upper phase of the mixture [C

2

mim]NTf

2

/6 M AlCl

3

at room temperature. Degreased in acetone in an ultrasonic bath, treated with dilute hydrochloric acid, and rinsed with distilled water.

Figure 13.9 SEM image of electrodeposited Al on mild steel formed potentiostatically at −0.75 V (vs Al) for 2 h in the upper phase of the mixture [C

4

mpyr]NTf

2

/2 M AlCl

3

at 100 °C.

Figure 13.10 SEM image of electrodeposited Al on gold formed potentiostatically at −0.45 V (vs Al) for 2 h in the upper phase of the mixture [C

4

mpyr]NTf

2

/1.6 M AlCl

3

) at 100 °C.

Figure 13.11 XRD patterns of an electrodeposited Al layer obtained potentiostatically at −1.7 V for 2 h in the upper phase of the mixture [C

4

mpyr]NTf

2

/1.6 M AlCl

3

at 100 °C on a glassy carbon substrate.

Figure 13.12 (a) SEM image of the electrodeposit formed potentiostatically on Pt in [C

4

mpyr]NTf

2

containing 0.25 M TaF

5

and 0.25 LiF at a potential of −1.8 V for 1 h at 200 °C. (b) XRD patterns of the deposited Ta layer.

Figure 13.13 SEM images showing the deposits gained from (a) choline chloride:ethylene glycol (1 : 2) + 0.3 M ZnCl

2

and (b) choline chloride:ethylene glycol (1 : 2) + 0.3 M 1 molar equivalent ethylene diamine. Both experiments were carried out by applying a constant current density of 5 mA cm

−2

at 50 °C, without stirring for 60 min.

Figure 13.14 Ni deposit obtained from bulk electrodeposition of choline chloride/ethylene-glycol containing 1.14 mol dm

−3

NiCl

2

·6H

2

O at 80 °C for 1 h on a nickel electrode at a current density of 1.5 A dm

−3

.

List of Tables

Synthesis of Ionic Liquids

Table 2.1.1 Physical data of selected ionic liquids

Table 2.2.1 Dependence of selected physicochemical properties (at 20 °C) of ionic liquids [EMIM]X on the anion X

−

Table 2.2.2 A comparison of the relative hydrophobicity of eight ionic liquids

Table 2.3.1 Freezing temperature data for a variety of metal salts and amides when mixed with choline chloride in 2 : 1 ratio

Table 2.3.2 Viscosity and conductivity of a variety of ionic liquids at 298 K

Chapter 3: Physical Properties of Ionic Liquids for Electrochemical Applications

Table 3.1 Melting points (°C) of several salts

Table 3.2 Melting points (

T

m

) of a series of [Tf

2

N]-type ILs

Table 3.3 Thermal properties of imidazolium-type ILs containing various anions

Table 3.4 Heat capacity and conductivity of ILs

Table 3.5 Viscosity of several ILs at room temperature (25 °C ± 1) and organic solvents (as a reference)

Table 3.6 Density of several ILs

Table 3.7 Refractive index of ILs

Table 3.8 The values of E

T

(30) and for some ILs

Table 3.9 Kamlet–Taft parameters for typical ILs

Table 3.10 Polarity of ILs determined by and Nile red

Table 3.11 Distribution ratios between RTIL/aqueous phases

Table 3.12 Observed solubility constants (

K

s

) of inorganic salts in several ILs

Table 3.13 Distribution ratio for Hg

2+

and Cd

2+

in the mixed systems of water and TSIL 1 or TSIL 2

Table 3.14 Electrochemical windows for a variety of ILs

Table 3.15 Specific ionic conductivity and related properties of imidazolium salts at 25 °C

Table 3.16 Ionic conductivity (25°C) of amines neutralized by HBF

4

Table 3.17 Ionic conductivity of ILs containing lithium salts at 25 °C

Table 3.18 Ionic conductivity of zwitterions containing equimolar lithium salts

Table 3.19 Physical properties and diffusion coefficients of ILs at 30 °C

Chapter 5: Electrodeposition of Alloys

Table 5.1 Metal alloys that have been electrodeposited from ionic liquids.

Chapter 6: Electrodeposition of Semiconductors from Ionic Liquids

Table 6.1 Semiconductors that have been deposited in ionic liquids

Chapter 8: Nanostructured Materials

Table 8.1.1 Effect of different additives on the crystallite size (electrolyte: 63 mol % absolute dry AlCl

3

, 37 mol % [C

2

mim]Cl, DC: 5 mA cm

− 2

, additive concentration: 4 wt %)

Table 8.1.2 The influence of different process parameters on the nanostructure of aluminum deposits

Table 8.1.3 Saturation magnetization, relative remanence, and coercivity for different crystallite sizes of nanostructured iron

Chapter 11: Impedance Spectroscopy

Table 11.1 Impedance response of common electrical and electrochemical elements

Chapter 12: Technical Aspects

Table 12.1 A cross section of the different types of reference electrodes that have been used by various researchers in a range of different RTILs

Electrodeposition from Ionic Liquids

Edited by Frank Endres, Andrew Abbott, and Douglas MacFarlane

Second, Completely Revised and Enlarged Edition

Editors

Prof. Frank Endres

Technical University Clausthal

Institute of Metallurgy

Robert-Koch-Str. 42

38678 Clausthal-Zellerfeld

Germany

Prof. Andrew Abbott

University of Leicester

Chemistry Department

LE1 7RH Leicester

United Kingdom

Prof. Douglas MacFarlane

Monash University

School of Chemistry

3800 Clayton

Victoria

Australia

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Print ISBN: 978-3-527-33602-9

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Cover Design Grafik-Design Schulz

List of Contributors

Andrew P. Abbott

University of Leicester

Department of Chemistry

University Road

Leicester LE1 7RH

UK

Rob Atkin

University of Newcastle

Priority Research Centre for Advanced Fluids and Interfaces

Callaghan Campus, University Drive

Callaghan, NSW 2308

Australia

Marco Balabajew

University of Marburg

Department of Chemistry

Hans-Meerwein-Strasse 4

35032 Marburg

Germany

Tom Beyersdorff

IoLiTec Ionic Liquids Technologies GmbH

Salzstraße 184

74076 Heilbronn

Germany

Natalia Borisenko

Clausthal University of Technology

Institute of Electrochemistry

Arnold-Sommerfeld-Street 6

38678 Clausthal-Zellerfeld

Germany

Timo Carstens

Clausthal University of Technology

Institute of Electrochemistry

Arnold-Sommerfeld-Street 6

38678 Clausthal-Zellerfeld

Germany

Po-Yu Chen

Kaohsiung Medical University

Department of Medicinal and Applied Chemistry

100 Shih-Chuan 1st Road

80708 Kaohsiung

Taiwan

Sherif Zein El Abedin

Clausthal University of Technology

Institute of Electrochemistry

Arnold-Sommerfeld-Street 6

38678 Clausthal-Zellerfeld

Germany

National Research Centre

Physical Chemistry Department, Electrochemistry and Corrosion Laboratory

El Bohouth Street 33, Dokki

12622 Giza

Egypt

Aaron Elbourne

University of Newcastle

Priority Research Centre for Advanced Fluids and Interfaces

Callaghan Campus

University Drive

Callaghan, NSW 2308

Australia

Frank Endres

Clausthal University of Technology

Institute of Electrochemistry

Arnold-Sommerfeld-Street 6

38678 Clausthal-Zellerfeld

Germany

Gero Frisch

Technische Universität Bergakademie Freiberg

Institut für Anorganische Chemie

Leipziger Straße 29

09596 Freiberg

Germany

René Gustus

Clausthal University of Technology

Institute of Electrochemistry

Arnold-Sommerfeld-Street 6

38678 Clausthal-Zellerfeld

Germany

Jennifer Hartley

Technische Universität Bergakademie Freiberg

Institut für Anorganische Chemie

Leipziger Straße 29

09596 Freiberg

Germany

Rolf Hempelmann

Universät des Saarlandes

Transferzentrum Nano-Elektrochemie

Campus Dudweiler Am Markt – Zeile 3

66125 Saarbrücken

Germany

Jürgen Janek

Justus-Liebig-Universität Gießen

Physikalisch-Chemisches Institut

Heinrich-Buff-Ring 17

35392 Gießen

Germany

Wrya Karim

Monash University, School of Chemistry

Wellington Road

Clayton, VIC 3800

Australia

Abhishek Lahiri

Clausthal University of Technology

Institute of Electrochemistry

Arnold-Sommerfeld-Street 6

38678 Clausthal-Zellerfeld

Germany

Hua Li

University of Newcastle

Priority Research Centre for Advanced Fluids and Interfaces

Callaghan Campus, University Drive

Callaghan, NSW 2308

Australia

Yao Li

Center for Composite Materials

Harbin Institute of Technology

150001 Harbin

China

Douglas R. Macfarlane

Monash University

School of Chemistry

Wellington Road

Clayton, VIC 3800

Australia

Katy J. McKenzie

University of Leicester

Department of Chemistry

University Road

Leicester LE1 7RH

UK

Sebastian A. Meiss

Justus-Liebig-Universität Gießen

Physikalisch-Chemisches Institut

Heinrich-Buff-Ring 17

35392 Gießen

Germany

Harald Natter

Universät des Saarlandes

Transferzentrum Nano-Elektrochemie

Campus Dudweiler Am Markt – Zeile 3

66125 Saarbrücken

Germany

Hiroyuki Ohno

Tokyo University of Agriculture and Technology

Graduate School of Engineering

2-24 Nakacho

Koganei

Tokyo 184-8588

Japan

Will Pitner

Merck KG&A

PLS R&D LSS Ionic Liquids 1

Frankfurter Str 250

64271 Darmstadt

Germany

Manuel Pölleth

Justus-Liebig-Universität Gießen

Physikalisch-Chemisches Institut

Heinrich-Buff-Ring 17

35392 Gießen

Germany

Jennifer M. Pringle

Deakin University, Geelong

Institute for Frontier Materials, Australian Centre of Excellence for Electromaterials Science

Burwood Campus, Burwood Highway

Burwood, VIC 3125

Australia

Giridhar Pulletikurthi

Clausthal University of Technology

Institute of Electrochemistry

Arnold-Sommerfeld-Street 6

38678 Clausthal-Zellerfeld

Germany

Marcus Rohnke

Justus-Liebig-Universität Gießen

Physikalisch-Chemisches Institut

Heinrich-Buff-Ring 17

35392 Gießen

Germany

Bernhard Roling

University of Marburg

Department of Chemistry

Hans-Meerwein-Strasse 4

35032 Marburg

Germany

Karl S. Ryder

University of Leicester

Department of Chemistry

University Road

Leicester LE1 7RH

UK

Thomas J. S. Schubert

IoLiTec Ionic Liquids Technologies GmbH

Salzstraße 184

74076 Heilbronn

Germany

I-Wen Sun

National Cheng Kung University

Department of Chemistry

1 Ta-Hsueh Road

Tainan 70101

Taiwan

Jorg Thöming

UFT

Section of Chemical Engineering

Universität Bremen, Leobener Str.

28359 Bremen

Germany

Jens Wallauer

University of Marburg

Department of Chemistry

Hans-Meerwein-Strasse 4

35032 Marburg

Germany

Urs Welz-Biermann

New Business-Chemicals/Ionic Liquids (NB-C)

Merck KG&A, NB-C, D1/311

Frankfurter Str 250

64293 Darmstadt

Germany

Jiupeng Zhao

School of Chemistry and Chemical Engineering

Harbin Institute of Technology

150001 Harbin

China

Dr. Daniel Waterkamp

bluesign technologies ag Moevenstrasse 18

9015 St.GallenSwitzerland

Abbreviations

Ionic Liquids

GNCS

guanidinium thiocyanate

GRTIL

gemini room-temperature ionic liquid

[HI-AA]

hydrophobic derivatized amino acid

IL

ionic liquid

poly(GRTIL)

polymerized gemini room-temperature ionic liquid

poly(RTIL)

polymerized room-temperature ionic liquid

RTIL

room-temperature ionic liquid

[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

[C

2

im]

+

1-ethylimidazolium

[C

1

mim]

+

1,3-dimethylimidazolium

[C

2

mim]

+

or [EMIM]

+

1-ethyl-3-methylimidazolium

[C

3

mim]

+

1-propyl-3-methylimidazolium

[

i

-C

3

mim]

+

1-isopropyl-3-methylimidazolium

[C

4

mim]

+

1-butyl-3-methylimidazolium

[

i

-C

4

mim]

+

1-isobutyl-3-methylimidazolium

[

s

-C

4

mim]

+

1-

sec

-butyl-3-methylimidazolium

[

t

C

4

mim]

+

1-

tert

-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

1

C

1

mim]

+

1,2,3-trimethylimidazolium

[C

2

C

1

mim]

+

1-ethyl-2,3-dimethylimidazolium

[C

3

C

1

mim]

+

1-propyl-2,3-dimethylimidazolium

[C

8

C

3

im]

+

1-octyl-3-propylimidazolium

[C

12

C

12

im]

+

1,3-bis(dodecyl)imidazolium

[C

1

OC

2

mim]

+

1-(2-methoxyethyl)-3-methyl-3

H

-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

2

F

3

mim]

+

1-trifluoroethyl-3-methylimidazolium

[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]

+

polymerizable 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

2

mpyr]

+

1-ethyl-1-methylpyrrolidinium

[C

3

mpyr]

+

1-propyl-1-methylpyrrolidinium

[C

4

mpyr]

+

1-butyl-1-methylpyrrolidinium

[C

6

mpyr]

+

1-hexyl-1-methylpyrrolidinium

[C

6

(dma)

γ

py]

+

1-hexyl-4-dimethylaminopyridinium

[C

1

C

3

pip]

+

1-methyl-1-propylpiperidinium

[C

2

C

6

pip]

+

1-ethyl-1-hexylpiperidinium

[C

8

quin]

+

1-octylquinolinium

[DMPhim]

+

1,3-dimethyl-2-phenylimidazolium

[EtNH

3

]

+

ethylammonium

[FcC

1

mim]

+

1-ferrocenylmethylimidazolium

[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

[HN

2 2 2

]

+

triethylammonium

[N

1 1 1 2OH

]

+

cholinium

[N

1 1 2 2OH

]

+

ethyl(2-hydroxyethyl)dimethylammonium

[N

1 1 1 4

]

+

trimethylbutylammonium

[N

1 4 4 4

]

+

methyltributylammonium

[N

1 8 8 8

]

+

methyltrioctylammonium

[N

4 4 4 4

]

+

tetrabutylammonium

[N

6 6 6 14

]

+

trihexyl(tetradecyl)ammonium

[NR

3

H]

+

trialkylammonium

[P

2 2 2(1O1

)]

+

triethyl(methoxymethyl)phosphonium

[P

4 4 4 3a

]

+

(3-aminopropyl)tributylphosphonium

[P

4 4 4 4

]

+

tetrabutylphosphonium

[P

6 6 6 14

]

+

trihexyl(tetradecyl)phosphonium

[P

8 8 8 14

]

+

tetradecyl(trioctyl)phosphonium

[PhCH

2

eim]

+

1-benzyl-2-ethylimidazolium

[pyH]

+

pyridinium

[S

2 2 2

]

+

triethylsulfonium

Anions

[Ace]

−

acetate

[Ala]

−

alaninate

[βAla]

−

β-alaninate

[Al(hfip)

4

]

−

tetra(hexafluoroisopropoxy)aluminate(III)

[Arg]

−

arginate

[Asn]

−

asparaginate

[Asp]

−

asparatinate

[BBB]

−

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

O,O

′]borate

[C

1

CO

2

]

−

ethanoate

[C

1

SO

4

]

−

, [O

3

SOC

1

]

−

methyl sulfate

[C

8

SO

4

]

−

, [O

3

SOC

8

]

−

octyl sulfate

[C

n

SO

4

]

−

alkyl sulfate

[(C

n

)(C

m

)SO

4

]

−

asymmetrical dialkyl sulfate

[(C

n

)

2

SO

4

]

−

symmetrical dialkyl sulfate

[CTf

3

]

−

tris{(trifluoromethyl)sulfonyl}methanide

[Cys]

−

cysteinate

[dbsa]

−

dodecylbenzenesulfonate

[dca]

−

dicyanamide

[FAP]

−

tris(pentafluoroethyl)trifluorophosphate

[Gln]

−

glutaminate

[Glu]

−

glutamate

[Gly]

−

glycinate anion

[His]

−

histidinate

[Ile]

−

isoleucinate

[lac]

−

lactate

[Leu]

−

leucinate

[Lys]

−

lysinate

[Met]

−

methionate

[Nle]

−

norleucinate

[NDf

2

]

−

bis{bis(pentafluoroethyl)phosphinyl}amide also known as bis{bis(pentafluoroethyl)phosphinyl}imide)

[NPf

2

]

−

, [BETI]

−

bis{(pentafluoroethyl)sulfonyl}amide also known as bis{(pentafluoroethyl)sulfonyl}imide

[NTf

2

]

−

, [TFSI]

−

bis{(trifluoromethyl)sulfonyl}amide also known as bis{(trifluoromethyl)sulfonyl}imide)

[O

2

CC

1

]

−

ethanoate

[O

3

SOC

2

]

−

, [O

3

SOC

2

]

−

ethylsulfate

[OMs]

−

methanesulfonate (mesylate)

[ONf]

−

perfluorobutylsulfonate

[OTf]

−

trifluoromethanesulfonate

[OTs]

−

4-toluenesulfonate, [4-CH

3

C

6

H

4

SO

3

]

−

(tosylate)

[Phe]

−

phenylalaninate

[Pro]

−

prolinate

[Sacc]

−

saccharinate

[Ser]

−

serinate

[Suc]

−

succinate

[tfpb]

−

tetrakis(3,5-bis(trifluoromethyl)phenyl)borate

[Thr]

−

threoninate

[Tos]

−

tosylate

[Trp]

−

tryptophanate

[Tyr]

−

tyrosinate

[Val]

−

valinate

Techniques

AA

all-atom parametrization

AES

Auger electron spectroscopy

AFM

atomic force microscopy

AMBER

assisted model building with energy refinement

ANN

associative neural network

APPLE&P

atomistic polarizable potential for liquids, electrolytes, and polymers

ARXPS

angle-resolved X-ray photoelectron spectroscopy

ATR-IR

attenuated total reflectance–infrared spectroscopy

BPNN

backpropagation neural network

BPP

Bloembergen, Purcell, and Pound theory

CADM

computer-aided design modeling

CC

Cole–Cole model

CCC

countercurrent chromatography

CD

Cole–Davidson model

CE

capillary electrophoresis

CEC

capillary electrochromatography

CHARMM

Chemistry at HARvard Molecular Mechanics

COSMO-RS

COnductor-like Screening MOdel for Real Solvents

COSY

COrrelation SpectroscopY

CPCM

conductor-like polarizable continuum model

CPMD

Car–Parrinello molecular dynamics

DFT

density functional theory

DLVO

Derjaguin and Landau, Verwey and Overbeek theory

DRS

dielectric relaxation spectroscopy

DSC

differential scanning calorimetry

ECSEM

electrochemical scanning electron microscopy

EC-XPS

electrochemical X-ray photoelectron spectroscopy

EF-CG

effective force coarse-graining method

EFM

effective fragment potential method

EI

electron ionization

EIS

electrochemical impedance spectroscopy

EMD

equilibrium molecular dynamics

EOF

electro-osmotic flow

EPSR

empirical potential structure refinement

ES

electrospray mass spectrometry

ESI–MS

electrospray ionization mass spectrometry

EXAFS

extended X-ray absorption fine structure

FAB

fast atom bombardment

FMO

fragment molecular orbital method

FIR

far-infrared spectroscopy

FTIR

Fourier transform infrared spectroscopy

GAMESS

general atomic and molecular electronic structure system

GC

gas chromatography

GGA

generalized gradient approximations

GLC

gas–liquid chromatography

GSC

gas–solid chromatography

HM

heuristic method

HOESY

heteronuclear Overhauser effect spectroscopy

HPLC

high-performance liquid chromatography

HREELS

high-resolution electron energy loss spectroscopy

IGC

inverse gas chromatography

IPES

inverse photoelectron spectroscopy

IR

infrared spectroscopy

IRAS

infrared reflection absorption spectroscopy

IR-VIS SFG

infrared–visible sum frequency generation

ISS

ion scattering spectroscopy

LEIS

low-energy ion scattering

L-SIMS

liquid secondary ion mass spectrometry

MAES

metastable atom electron spectroscopy

MALDI

matrix-assisted laser desorption

MBSS

molecular beam surface scattering

MC

Monte Carlo

MD

molecular dynamics

MIES

metastable impact electron spectroscopy

MLP

multilayer perceptron

MLR

multilinear regression

MM

molecular mechanics

MR

magnetic resonance

MRI

magnetic resonance imaging

MS

mass spectrometry

NEMD

nonequilibrium molecular dynamics

NEXAFS

near-edge absorption fine structure

NIR

near-infrared spectroscopy

NMR

nuclear magnetic resonance

NR

neutron reflectivity

NRTL

nonrandom two liquid

OPLS

optimized potentials for liquid simulations

PCM

polarizable continuum model

PDA

photodiode array detection

PES

photoelectron spectroscopy

PFG-NMR

pulsed field-gradient nuclear magnetic resonance

PGSE-NMR

pulsed-gradient spin-echo nuclear magnetic resonance

PPR

projection pursuit regression

QM

quantum mechanics

OPLS

optimized potentials for liquid simulations

QSAR

quantitative structure–activity relationship

QSPR

quantitative structure–property relationship

RAIRS

reflection absorption infrared spectroscopy

RI

refractive index

RMC

reverse Monte Carlo

RNEMD

reverse nonequilibrium molecular dynamics

RNN

recursive neural network

ROESY

rotating-frame Overhauser effect spectroscopy

RP-HPLC

reversed-phase high-performance liquid chromatography

RST

regular solution theory

SANS

small-angle neutron scattering

SCMFT

self-consistent mean-field theory

SEM

scanning electron microscopy

SEM-EDX

scanning electron microscopy with energy-dispersive X-ray

SFA

surface force apparatus

SFC

supercritical fluid chromatography

SFG

sum-frequency generation

SFM

systematic fragmentation method

SIMS

secondary ion mass spectrometry

soft-SAFT

soft statistical associating fluid theory

STM

scanning tunneling microscopy

SVN

support vector network

TEM

transmission electron microscopy

TGA

thermogravimetric analysis

THz-TDS

terahertz time-domain spectroscopy

TLC

thin-layer chromatography

tPC-PSAFT

truncated perturbed chain–polar statistical associating fluid theory

TPD

temperature-programmed desorption

UA

united-atom parametrization

UHV

ultrahigh vacuum

UNIFAC

UNI

QUAC

F

unctional-group

A

ctivity

C

oefficients

UNIQUAC

UNI

versal

QUA

si

C

hemical

UPLC

ultra-performance liquid chromatography

UPS

ultraviolet photoelectron spectroscopy

UV

ultraviolet

UV-vis

ultraviolet–visible

VBT

volume-based thermodynamics

XPS

X-ray photoelectron spectroscopy

XRD

X-ray diffraction

XRR

X-ray reflectivity

Miscellaneous

Å

1 Ångstrom = 10

−10

m

ACS

American Chemical Society

ANQ

1-amino-3-nitroguanidine

API

active pharmaceutical ingredient

ATMS

acetyltrimethylsilane

ATPS

aqueous two-phase system

a.u.

atomic units

BASF™

Badische Anilin- und Soda-Fabrik

BASIL

Biphasic Acid Scavenging utilizing Ionic Liquids

BATIL

Biodegradability and Toxicity of Ionic Liquids

BE

binding energy

BILM

bulk ionic liquid membrane

BNL

Brookhaven National Laboratory

BOD

biochemical oxygen demand

BP

British Petroleum

b.pt.

boiling point

BSA

bovine serum albumin

BT

benzothiophene

BTAH

benzotriazole

BTX

benzene–toluene–xylene mixture

calc.

calculated

CB

Cibacron Blue 3GA

CCDC

Cambridge Crystallographic Data Centre

CE

crown ether

CEES

2-chloroethyl ethyl sulfide

CFC MC

“continuous fractional component” Monte Carlo

CL&P

Canongia Lopes and Pádua

CLM

charge lever momentum

CMC

critical micelle concentration

CMPO

octyl(phenyl)-

N,N

-diisobutylcarbamoylmethylphosphine oxide

[C

n

MeSO

4

]

alkyl methyl sulfate

CNTs

carbon nanotubes

COIL

Congress on Ionic Liquids

CPU

central processing unit

CSA

chemical shielding anisotropy

CSD

Cambridge Structural Database

CWAs

chemical warfare agents

d

doublet (NMR)

bond energy at 298 K

1D

one-dimensional

2D

two-dimensional

3D

three-dimensional

DABCO

1,4-diazabicyclo[2.2.2]octane

DBT

dibenzothiophene

DC

direct current

DC18C6

dicyclohexyl-18-crown-6

DF

Debye and Falkenhagen

DH

Debye–Hückel

DIIPA

diisopropylamine

4,6-DMDBT

4,6-dimethyldibenzothiophene

DNA

deoxyribonucleic acid

DMF

dimethylmethanamide (dimethylformamide)

DMH

dimethylhexene

2DOM

two-dimensional ordered macroporous

3DOM

three-dimensional ordered macroporous

DOS

density of states

DPC

diphenylcarbonate

DRA

drag-reducing agent

DSSC

dye-sensitized solar cell

DSTE

double-stimulated echo

E

enrichment

EDC

extractive distillation column

EE

expanded ensemble approach

EoS

equation of state

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

FMF

Freiburger Materialforschungszentrum

FRIAS

Freiburg Institute of Advanced Studies

FSE

full-scale error

ft

foot

GDDI

generalized distributed data interface

GEMC

Gibbs ensemble Monte Carlo

GSSG

glutathione disulfide

GSH

glutathione

GT

gauche-trans

HDS

hydrodesulfurization

HEMA

2-(hydroxyethyl) methacrylate

HOMO

highest occupied molecular orbital

HOPG

highly oriented pyrolytic graphite

HV

high vacuum

i.d.

inner diameter

IFP

Institute Français du Pétrole

IgG

immunoglobulin G

IPBE

ion-pair binding energy

IPE

Institute of Process Engineering, Chinese Academy of Sciences, Beijing

ITO

indium-tin oxide

IUPAC

International Union of Pure and Applied Chemistry

IVR

intramolecular vibrational energy redistribution

J

coupling constant (NMR)

KWW

Kohlrausch–Williams–Watts

LCEP

lower critical end point

LCST

lower critical separation temperature

LEAF

Laser Electron Accelerator Facility

LF-EoS

lattice-fluid model equation of state

LLE

liquid–liquid equilibria

LMOG

low-molecular-weight gelator

LSERs

linear solvation energy relationships

LUMO

lowest unoccupied molecular orbital

m

multiplet (NMR)

M

molar concentration

MBI

1-methylbenzimidazole

MCH

methylcyclohexane

MDEA

methyl diethanolamine; bis(2-hydroxyethyl)methylamine

MEA

monoethanolamine; 2-aminoethanol

MFC

minimal fungicidal concentrations

MIC

minimal inhibitory concentrations

MMM

mixed matrix membrane

MNDO

modified neglect of differential overlap

m.pt.

melting point

MSD

mean square displacement

3-MT

3-methylthiophene

MW

molecular weight

MWCNTs

multiwalled carbon nanotubes

m/z

mass-to-charge ratio

NBB

1-butylbenzimidazole

NCA

N

-carboxyamino acid anhydride

NE equation

Nernst–Einstein equation

NES

New Entrepreneur Scholarship

NFM

N

-formylmorpholine

NIP

neutral ion pair

NIT

neutral ion triplet

NMP

N

-methylpyrrolidone

NOE

nuclear Overhauser effect

NP

nanoparticle

NRTL

nonrandom two liquid

NRTL-SAC

nonrandom two-liquid segmented activity coefficients

o.d.

outer diameter

OECD

Organisation for Economic Co-operation and Development

OKE

optical Kerr effect

p

pressure

PAO

polyalphaolefin

PBT

persistent, bioaccumulative, and toxic

PDMS

polydimethoxysilane

PEDOT

poly(3,4-ethylenedioxythiophene)

PEG

poly(ethyleneglycol)

PEM

polymer-electrolyte membrane

PEN

poly(ethylene-2,6-naphthalene decarboxylate)

PES

polyethersulfone

pH

−log

10

(a(H

+

)); a measure of the acidity of a solution

PIB

polyisobutene

p

K

a

−log

10

(

K

a

)

p

K

b

−log

10

(

K

b

)

PPDD

polypyridylpendant poly(amidoamine) dendritic derivative

ppm

parts per million

PQRE

platinum

quasi

-reference electrode

(PR)-EoS

Peng–Robinson equation of state

PS

polystyrene

PSE

process systems engineering

psi

1 pound per square inch = 6894.75729 Pa

PTC

phase transfer catalyst

PTFE

poly(tetrafluoroethylene)

PT

x

pressure–temperature composition

PZC

potential of zero charge

r

bond length

RDC

rotating disc contactor

RDF

radial distribution function

REACH

Registration, Evaluation, Authorisation, and restriction of CHemical substances

RF

radio frequency

(RK) EoS

Redlich–Kwong equation of state

RMSD

root-mean-square deviation

RT

room temperature

s

singlet (NMR)

S

entropy

scCO

2

supercritical carbon dioxide

SCILL

Solid catalyst with ionic liquid layer

SDS

sodium dodecyl sulfate

SE

spin echo

SED

Stokes–Einstein–Debye equation

S/F

solvent-to-feed ratio

SHOP

Shell higher olefin process

SILM

supported ionic liquid membrane

SILP

supported ionic liquid phase

SLE

solid–liquid equilibrium

SLM

supported liquid membrane

STE

stimulated spin echo

SVHC

substance of very high concern

t

triplet (NMR)

TBP

4-(

t

-butyl)pyridine

TCEP

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

TEA

triethylamine

TEGDA

tetra(ethylene glycol) diacrylate

THF

tetrahydrofuran

TIC

toxic industrial chemical

TMB

trimethylborate

TMP

trimethylpentene

TMPD

N,N,N′N′

-tetramethyl-

p

-phenylenediamine

TOF

time-of-flight

TT

trans–trans

UCEP

upper critical end point

UCST

upper critical solution temperature

UHV

ultrahigh vacuum

VFT

Vogel–Fulcher–Tammann equations

VLE

vapor–liquid equilibria

VLLE

vapor–liquid–liquid equilibria

VMP

variable multichannel potentiostat

VOCs

volatile organic compounds