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This paper is published as part of a PCCP Themed Issue on:
Physical Chemistry of Ionic Liquids
Guest Editor: Frank Endres (Technical University of Clausthal, Germany)
Editorial
Physical chemistry of ionic liquids
Phys. Chem. Chem. Phys., 2010, DOI: 10.1039/c001176m
Perspectives
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Ionicity in ionic liquids: correlation with ionic structure and
physicochemical properties
Kazuhide Ueno, Hiroyuki Tokuda and Masayoshi Watanabe,
Phys. Chem. Chem. Phys., 2010, DOI: 10.1039/b921462n
Design of functional ionic liquids using magneto- and
luminescent-active anions
Yukihiro Yoshida and Gunzi Saito, Phys. Chem. Chem. Phys.,
2010, DOI: 10.1039/b920046k
Accelerating the discovery of biocompatible ionic liquids
Nicola Wood and Gill Stephens, Phys. Chem. Chem. Phys.,
2010, DOI: 10.1039/b923429b
Ionic liquids and reactions at the electrochemical interface
Douglas R. MacFarlane, Jennifer M. Pringle, Patrick C. Howlett
and Maria Forsyth, Phys. Chem. Chem. Phys., 2010,
DOI: 10.1039/b923053j
Photochemical processes in ionic liquids on ultrafast
timescales
Chandrasekhar Nese and Andreas-Neil Unterreiner, Phys.
Chem. Chem. Phys., 2010, DOI: 10.1039/b916799b
At the interface: solvation and designing ionic liquids
Robert Hayes, Gregory G. Warr and Rob Atkin, Phys. Chem.
Chem. Phys., 2010, DOI: 10.1039/b920393a
Ionic liquids in surface electrochemistry
Hongtao Liu, Yang Liu and Jinghong Li, Phys. Chem. Chem.
Phys., 2010, DOI: 10.1039/b921469k
Discussion
Do solvation layers of ionic liquids influence electrochemical
reactions?
Frank Endres, Oliver Höfft, Natalia Borisenko, Luiz Henrique
Gasparotto, Alexandra Prowald, Rihab Al-Salman, Timo Carstens,
Rob Atkin, Andreas Bund and Sherif Zein El Abedin, Phys. Chem.
Chem. Phys., 2010, DOI: 10.1039/b923527m
Papers
Plasma electrochemistry in ionic liquids: deposition of
copper nanoparticles
M. Brettholle, O. Höfft, L. Klarhöfer, S. Mathes, W. Maus-
Friedrichs, S. Zein El Abedin, S. Krischok, J. Janek and F.
Endres, Phys. Chem. Chem. Phys., 2010,
DOI: 10.1039/b906567a
Size control and immobilization of gold nanoparticles
stabilized in an ionic liquid on glass substrates for plasmonic
applications
Tatsuya Kameyama, Yumi Ohno, Takashi Kurimoto, Ken-ichi
Okazaki, Taro Uematsu, Susumu Kuwabata and Tsukasa
Torimoto, Phys. Chem. Chem. Phys., 2010,
DOI: 10.1039/b914230d
Electrostatic properties of liquid 1,3-dimethylimidazolium
chloride: role of local polarization and effect of the bulk
C. Krekeler, F. Dommert, J. Schmidt, Y. Y. Zhao, C. Holm, R.
Berger and L. Delle Site, Phys. Chem. Chem. Phys., 2010,
DOI: 10.1039/b917803c
Selective removal of acetylenes from olefin mixtures through
specific physicochemical interactions of ionic liquids with
acetylenes
Jung Min Lee, Jelliarko Palgunadi, Jin Hyung Kim, Srun Jung,
Young-seop Choi, Minserk Cheong and Hoon Sik Kim, Phys.
Chem. Chem. Phys., 2010, DOI: 10.1039/b915989d
Screening of pairs of ions dissolved in ionic liquids
R. M. Lynden-Bell, Phys. Chem. Chem. Phys., 2010,
DOI: 10.1039/b916987c
Double layer, diluent and anode effects upon the
electrodeposition of aluminium from chloroaluminate based
ionic liquids
Andrew P. Abbott, Fulian Qiu, Hadi M. A. Abood, M. Rostom Ali
and Karl S. Ryder, Phys. Chem. Chem. Phys., 2010,
DOI: 10.1039/b917351j
A comparison of the cyclic voltammetry of the Sn/Sn(II)
couple in the room temperature ionic liquids N-butyl-N-
methylpyrrolidinium dicyanamide and N-butyl-N-
methylpyrrolidinium bis(trifluoromethylsulfonyl)imide:
solvent induced changes of electrode reaction mechanism
Benjamin C. M. Martindale, Sarah E. Ward Jones and Richard G.
Compton, Phys. Chem. Chem. Phys., 2010,
DOI: 10.1039/b920217j
Ionic liquids through the looking glass: theory mirrors
experiment and provides further insight into aromatic
substitution processes
Shon Glyn Jones, Hon Man Yau, Erika Davies, James M. Hook,
Tristan G. A. Youngs, Jason B. Harper and Anna K. Croft, Phys.
Chem. Chem. Phys., 2010, DOI: 10.1039/b919831h
Nitrile-functionalized pyrrolidinium ionic liquids as solvents
for cross-coupling reactions involving in situ generated
nanoparticle catalyst reservoirs
Yugang Cui, Ilaria Biondi, Manish Chaubey, Xue Yang, Zhaofu
Fei, Rosario Scopelliti, Christian G. Hartinger, Yongdan Li, Cinzia
Chiappe and Paul J. Dyson, Phys. Chem. Chem. Phys., 2010,
DOI: 10.1039/b920025h
Ionic liquid as plasticizer for europium(III)-doped luminescent
poly(methyl methacrylate) films
Kyra Lunstroot, Kris Driesen, Peter Nockemann, Lydie Viau, P.
Hubert Mutin, André Vioux and Koen Binnemans, Phys. Chem.
Chem. Phys., 2010, DOI: 10.1039/b920145a
Ab initio study on SN2 reaction of methyl p-
nitrobenzenesulfonate and chloride anion in [mmim][PF6]
Seigo Hayaki, Kentaro Kido, Hirofumi Sato and Shigeyoshi
Sakaki, Phys. Chem. Chem. Phys., 2010,
DOI: 10.1039/b920190b
Influence of imidazolium bis(trifluoromethylsulfonylimide)s
on the rotation of spin probes comprising ionic and hydrogen
bonding groups
Veronika Strehmel, Hans Rexhausen and Peter Strauch, Phys.
Chem. Chem. Phys., 2010, DOI: 10.1039/b920586a
Thermo-solvatochromism in binary mixtures of water and
ionic liquids: on the relative importance of solvophobic
interactions
Bruno M. Sato, Carolina G. de Oliveira, Clarissa T. Martins and
Omar A. El Seoud, Phys. Chem. Chem. Phys., 2010,
DOI: 10.1039/b921391k

Patterns of protein unfolding and protein aggregation in ionic
liquids
Diana Constatinescu, Christian Herrmann and Hermann
Weingärtner, Phys. Chem. Chem. Phys., 2010,
DOI: 10.1039/b921037g
High vacuum distillation of ionic liquids and separation of
ionic liquid mixtures
Alasdair W. Taylor, Kevin R. J. Lovelock, Alexey Deyko, Peter
Licence and Robert G. Jones, Phys. Chem. Chem. Phys., 2010,
DOI: 10.1039/b920931j
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Designer molecular probes for phosphonium ionic liquids
Robert Byrne, Simon Coleman, Simon Gallagher and Dermot
Diamond, Phys. Chem. Chem. Phys., 2010,
DOI: 10.1039/b920580b
States and migration of an excess electron in a pyridinium-
based, room-temperature ionic liquid: an ab initio molecular
dynamics simulation exploration
Zhiping Wang, Liang Zhang, Robert I. Cukier and Yuxiang Bu,
Phys. Chem. Chem. Phys., 2010, DOI: 10.1039/b921104g
J-aggregation of ionic liquid solutions of meso-tetrakis(4-
sulfonatophenyl)porphyrin
Maroof Ali, Vinod Kumar, Sheila N. Baker, Gary A. Baker and
Siddharth Pandey, Phys. Chem. Chem. Phys., 2010,
DOI: 10.1039/b920500d
Spontaneous product segregation from reactions in ionic
liquids: application in Pd-catalyzed aliphatic alcohol oxidation
Charlie Van Doorslaer, Yves Schellekens, Pascal Mertens, Koen
Binnemans and Dirk De Vos, Phys. Chem. Chem. Phys., 2010,
DOI: 10.1039/b920813p
Electrostatic interactions in ionic liquids: the dangers of
dipole and dielectric descriptions
Mark N. Kobrak and Hualin Li, Phys. Chem. Chem. Phys., 2010,
DOI: 10.1039/b920080k
Insights into the surface composition and enrichment effects
of ionic liquids and ionic liquid mixtures
F. Maier, T. Cremer, C. Kolbeck, K. R. J. Lovelock, N. Paape, P.
S. Schulz, P. Wasserscheid and H.-P. Steinrück, Phys. Chem.
Chem. Phys., 2010, DOI: 10.1039/b920804f
Ionic liquids and reactive azeotropes: the continuity of the
aprotic and protic classes
José N. Canongia Lopes and Luís Paulo N. Rebelo, Phys. Chem.
Chem. Phys., 2010, DOI: 10.1039/b922524m
A COSMO-RS based guide to analyze/quantify the polarity of
ionic liquids and their mixtures with organic cosolvents
José Palomar, José S. Torrecilla, Jesús Lemus, Víctor R. Ferro
and Francisco Rodríguez, Phys. Chem. Chem. Phys., 2010,
DOI: 10.1039/b920651p
Solid and liquid charge-transfer complex formation between
1-methylnaphthalene and 1-alkyl-cyanopyridinium
bis{(trifluoromethyl)sulfonyl}imide ionic liquids
Christopher Hardacre, John D. Holbrey, Claire L. Mullan, Mark
Nieuwenhuyzen, Tristan G. A. Youngs, Daniel T. Bowron and
Simon J. Teat, Phys. Chem. Chem. Phys., 2010,
DOI: 10.1039/b921160h
Blending ionic liquids: how physico-chemical properties
change
F. Castiglione, G. Raos, G. Battista Appetecchi, M. Montanino, S.
Passerini, M. Moreno, A. Famulari and A. Mele, Phys. Chem.
Chem. Phys., 2010, DOI: 10.1039/b921816e
View Article Online
NMR spectroscopic studies of cellobiose solvation in
EmimAc aimed to understand the dissolution mechanism of
cellulose in ionic liquids
Jinming Zhang, Hao Zhang, Jin Wu, Jun Zhang, Jiasong He and
Junfeng Xiang, Phys. Chem. Chem. Phys., 2010,
DOI: 10.1039/b920446f
Electrochemical carboxylation of -chloroethylbenzene in
ionic liquids compressed with carbon dioxide
Yusuke Hiejima, Masahiro Hayashi, Akihiro Uda, Seiko Oya,
Hiroyuki Kondo, Hisanori Senboku and Kenji Takahashi, Phys.
Chem. Chem. Phys., 2010, DOI: 10.1039/b920413j
A theoretical study of the copper(I)-catalyzed 1,3-dipolar
cycloaddition reaction in dabco-based ionic liquids: the anion
effect on regioselectivity
Cinzia Chiappe, Benedetta Mennucci, Christian Silvio Pomelli,
Angelo Sanzone and Alberto Marra, Phys. Chem. Chem. Phys.,
2010, DOI: 10.1039/b921204c
Fragility, Stokes–Einstein violation, and correlated local
excitations in a coarse-grained model of an ionic liquid
Daun Jeong, M. Y. Choi, Hyung J. Kim and YounJoon Jung,
Phys. Chem. Chem. Phys., 2010, DOI: 10.1039/b921725h
Reactions of excited-state benzophenone ketyl radical in a
room-temperature ionic liquid
Kenji Takahashi, Hiroaki Tezuka, Shingo Kitamura, Toshifumi
Satoh and Ryuzi Katoh, Phys. Chem. Chem. Phys., 2010,
DOI: 10.1039/b920131a
In search of pure liquid salt forms of aspirin: ionic liquid
approaches with acetylsalicylic acid and salicylic acid
Katharina Bica, Christiaan Rijksen, Mark Nieuwenhuyzen and
Robin D. Rogers, Phys. Chem. Chem. Phys., 2010,
DOI: 10.1039/b923855g
Nanocomposites of ionic liquids confined in mesoporous
silica gels: preparation, characterization and performance
Juan Zhang, Qinghua Zhang, Xueli Li, Shimin Liu, Yubo Ma, Feng
Shi and Youquan Deng, Phys. Chem. Chem. Phys., 2010,
DOI: 10.1039/b920556j
An ultra high vacuum-spectroelectrochemical study of the
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picolinium bis(trifluoromethylsulfonyl)imide
Fulian Qiu, Alasdair W. Taylor, Shuang Men, Ignacio J. Villar-
Garcia and Peter Licence, Phys. Chem. Chem. Phys., 2010,
DOI: 10.1039/b924985k
Understanding siloxane functionalised ionic liquids
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Hallett, Tom Welton, Andrew J. P. White and Patricia A. Hunt,
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On the electrodeposition of tantalum from three different
ionic liquids with the bis(trifluoromethyl sulfonyl) amide
anion
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Endres, Phys. Chem. Chem. Phys., 2010,
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Solid-state dye-sensitized solar cells using polymerized ionic
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Nobuo Tanabec and Masayoshi Watanabe, Phys. Chem. Chem.
Phys., 2010, DOI: 10.1039/b920633g
Dynamics of ionic liquid mediated quantised charging of
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Phys. Chem. Chem. Phys., 2010, DOI: 10.1039/b921368f
 PAPER www.rsc.org/pccp | Physical Chemistry Chemical Physics

Double layer, diluent and anode effects upon the electrodeposition

of aluminium from chloroaluminate based ionic liquids
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Andrew P. Abbott,a Fulian Qiu,a Hadi M. A. Abood,ab M. Rostom Aliac and

Karl S. Ryder*a
Received 22nd August 2009, Accepted 30th October 2009
First published as an Advance Article on the web 18th November 2009
DOI: 10.1039/b917351j

The deposition of aluminium from a chloroaluminate based ionic liquid was studied to elucidate
the effect of a diluent (toluene) and electrolyte (LiCl) on the deposit morphology. A wide variety
of analytical techniques was applied to this system to determine the speciation and mechanism of
material growth. These included: 27Al NMR, FAB-MS, cyclic voltammetry, chronocoulometry,
chronopotentiometry, scanning electron microscopy and atomic force microscopy. It was found
that under-potential deposition (upd) causes a change in the way in which metal grows on the
electrode surface. Metal grows in two regimes which are believed to be nano-material and bulk
material. The addition of toluene causes a change in speciation and a decrease in upd which in
turn changes the morphology of the deposit obtained and can lead to mirror finish aluminium.
The addition of LiCl has the opposite effect encouraging upd and leading to larger crystallites and
a dark grey deposit. It is also shown for the first time that under many conditions the rate of the
anodic dissolution process is overall rate controlling and one effect of the addition of toluene is to
increase the rate of anodic dissolution.

Introduction
The deposition of metals from ionic liquids has been studied
by a large number of groups and several reviews have recently
been written on the subject.1–4 While numerous metals have
been deposited from these media still relatively little is
known about the deposition mechanism and the effect of mass
transport and speciation.
Fundamentally, the mechanism of metal deposition in an
ionic liquid is different from that in aqueous solution because
of the significant differences in speciation, mass transport and
double layer structure. The absence of water affects the
chemistry of the anodic and cathodic processes both in terms
of competing reactions and oxide/hydroxide reactions with
metal ions. Of the systems investigated to date by far the most
commonly studied is aluminium from chloroaluminate
melts.5–7 It is surprising that the deposition of aluminium
from an ionic liquid has not been commercialised given the
strategic importance of the process and the fact that the
technology has been known for over 30 years. The majority
of studies have used pyridinium and imidazolium chlorides
mixed with AlCl3.8–10 A variety of electrode materials
have been studied but it was found that metal deposition
was only possible using Lewis acidic ionic liquids (i.e. the mole
fraction of AlCl3 in the mixture >0.5).4 Voltammetry and
potential step experiments have been used and these have
a
Department of Chemistry, University of Leicester, Leicester,
UK LE1 7RH. E-mail: k.s.ryder@le.ac.uk;
b
Fax: +44 (0)116 252 3789
Chemistry Department, College of science, Al-Nahrain University,
P.O.B. 64055 Jadria, Baghdad, Iraq
c
Department of Applied Chemistry and Chemical Technology,
University of Rajshahi, Rajshahi-6205, Bangladesh
shown that mass transfer and charge transfer both play a
role in governing nucleation.11,12 The deposits of aluminium
obtained are crystalline and the current density affects the
grain size. Several groups have shown that the metal is initially
deposited by progressive nucleation but no information
has been obtained on the mechanism of material growth
or the effect of external factors such as additives to the
ionic liquid.11–13 The addition of aromatic solvents to the
ionic liquids allows bright finishes to be obtained although
no studies have determined the cause of this morphology
change.
In the current work a range of analytical techniques are
applied to the BMIMCl–AlCl3–toluene–LiCl system to relate
the aluminium speciation to the electrochemical response
and the resulting deposit morphology arising from constant
potential deposition experiments.
Results and discussion
Fig. 1 shows a cyclic voltammogram of a Pt electrode in
BMIMCl–2AlCl3. The cathodic sweep has one dominant
reduction process (B) with a secondary underlying process
(A) at ca. 0.2 V. The anodic sweep has two clear corres-
ponding stripping processes (A 0 ) and (B 0 ). These have been
observed before although their cause has not been identified.
Fig. 2 shows the effect of sweeping the potential to increasingly
cathodic limits and it can be seen that the more cathodic limits
lead to increasing charge for the more anodic dissolution
process (B 0 ). The two peaks could be due to either alloy
formation with the Pt substrate or the deposition of aluminium
with two different morphologies. Since the shape of the
voltammogram is the same on an aluminium electrode the

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Fig. 1 Cyclic voltammograms recorded at 50 mV s1 using a 0.5 mm

Pt disc electrode in 2 : 1 AlCl3 : [BMIM]Cl neat, with 18 wt% toluene
and with 0.5 mol equivalent LiCl as indicated.

former idea can be discounted. The two different morphologies

must result from different growth mechanisms. One possibility
could be the initial growth of a large number of nuclei on the
surface, some of which stop growing giving a material with a
different morphology. Alternatively, some aspect of the
interfacial layer structure could neutralise the surface energy
of the growing particle. Endres et al. have shown14 that
different morphologies of aluminium can be grown from a
variety of ionic liquids. It was shown that pyrrolidinium
based ionic liquids led to nano-structured deposits whereas
imidazolium caused micro-crystalline deposits. This was
ascribed to a cation effect, which ultimately is a chemical
cause, although several other physical properties of the liquid
also change that could account for the observed differences in
morphology. Fig. 2 A series of cyclic voltammograms recorded at 50 mV s1 using
The cause of the cessation of growth in the BMIMCl– a 0.5 mm Pt disc electrode in (i) neat 2 : 1 acidic AlCl3 + [BMIM]Cl
2AlCl3 system is, however, unknown but a cation effect could ionic liquid, (ii) with 18 wt% toluene added. The voltammograms were
correlate with the latter of the above ideas. recorded at different cathodic vertex potentials: (a) 0.8 V, (b) 0.6 V,
The material that grows at larger overpotentials is bulk (c) 0.55 V, (d) 0.5 V, (e) 0.45 V, (f) 0.4 V and (g) 0.35 V.
aluminium with a dendritic morphology which can be seen
from visual inspection of the electrode upon prolonged electro- evidence that the original ideas regarding a two step deposition
lysis. Extrapolation of the second anodic peak back to zero process are correct.w
current produces a value of approximately 0.0 V vs. Al The growth of two different forms of aluminium could be due
confirming that it is associated with bulk aluminium. The to differences in mass transport, changes in speciation, double
material that is dissolved at (A 0 ) must be easier to strip from layer effects or surface energetics arising from different nucleation
the surface and this could be due to the material having a sites. The last of these options can be largely discounted as a
higher surface area than bulk aluminium. High surface energy major factor as the voltammetry is quite repeatable and relatively
is consistent with finely-divided metal. independent of the polishing procedure.
To prove that the two stripping peaks are due to bulk and
smaller scale deposition processes a sample was grown at 0.8 V
Effect of adding toluene
vs. Al for 300 s. An AFM image of the surface was taken and
this is shown in Fig. 3(a). It can be seen that the deposit Several groups have studied the effect of additives on the
contains both large and small crystallites. The process was morphology of aluminium deposits.15–18 Hussey et al. studied
repeated on a cleaned electrode but this time the potential was Lewis acidic AlCl3–EMIMCl ionic liquids [>50 mol% AlCl3]
held at 0.8 V vs. Al for 300 s and then scanned from 0.8 V and found that although aluminium could be electroplated
to +0.3 V at a potential scan rate of 5 mV s1i.e. the potential from the neat liquid, the quality of the electrodeposit is greatly
scan was stopped before the bulk material dissolved. The
AFM image of this sample is shown in Fig. 3(b) and it can w Scrupulous care was taken in the acquisition of these images to ensure
that they were representative of the general surface morphology.
be clearly seen that the small growths have dissolved while the Typically each region of the surface was sampled 5–10 times in order
larger crystallites remain on the surface. This is convincing to establish consistency.

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Fig. 3 AFM images of Al grown on a Pt substrate at 0.8 V versus Al
for (a) 300 s and (b) the same deposition procedure followed by
scanning potential from 0.8 V to +0.3 V at a potential scan rate
of 5 mV s1.
enhanced by the addition of benzene as a cosolvent.17 The
same group studied the deposition of Ag–Al alloys from
the same melt and found that the addition of benzene hindered
the adsorption of silver on the electrode surface. Attempts to
deposit Ni and Ni alloys from chloroaluminate melts found
that the addition of benzene (20 wt%) produced a bright
deposit at low current densities but a black, finely-divided
powder was produced at higher current densities.18 Osteryoung
and Robinson19 used potentiometry to study speciation and
concluded that because the addition of benzene to a butyl-
pyridinium–AlCl3 system did not cause a significant change in
the cell potential there was no change in speciation.
Fig. 1 shows the effect on the voltammetry following the
addition of 18 wt% toluene to the AlCl3–BMIMCl ionic
liquid. There is an increase in the charge associated with both
the deposition and stripping processes which shows that mass
transport may have an effect on metal growth rates. The
addition of toluene decreases the metal concentration from
5.9 mol dm3 to 4.4 mol dm3 but there is also a concomitant
decrease in the viscosity. While no viscosity data exist for this
exact system the corresponding system using benzene as a
diluent has been characterised and a 40% decrease in the
kinematic viscosity was observed for the same weight fraction
of benzene added to the ionic liquid.17
1864 | Phys. Chem. Chem. Phys., 2010, 12, 1862–1872
Speciation
Diluents could have two effects: the first is obviously the
decrease that they will cause in the solution viscosity and
metal concentration; the second is the change in speciation.
Here FAB-MS was used to determine the species present and
showed a variety of Al containing anions, the most common of
which was AlCl4. The presence of Al2Cl7 was also detected
along with traces of Al2OCl5 (although this could arise
because the material was transferred rapidly from the inert
environment to the MS ionisation chamber through an open
atmosphere). To determine the relative amounts of AlCl4 and
Al2Cl7 27Al NMR spectroscopy was carried out. 27Al NMR
spectroscopy was used as a nuclear probe to the Al speciation
in various compositions of Lewis acidic BMIM : AlCl3 eutectic
melts. Liquid compositions of 1.5 : 1 and 2.0 : 1 (AlCl3 : BMIMCl)
were examined with and without the presence of toluene
(30% v/vz) added as a diluent. In addition, a liquid sample
aged over 3 months from which only poor Al deposits were
obtained was examined and this was compared with a freshly
prepared liquid of the same composition.
Aluminium, 27Al, NMR spectra of the ionic liquids all
showed a broad peak centred around 111–110 ppm and in
each case it was clear from the line shape that this broad peak
was a combination of at least two other resonance peaks,
Fig. 4(a). In several cases it was also clear that the line widths
(s/ppm) of these components were disparate with one line very
much narrower than the other. This observation is consistent
with similar observations in other Al based ionic liquids;20
here the broad line (usually with the larger value of d/ppm)
was attributed to Al2Cl7, whereas the narrower line (with the
smaller value of d/ppm) was attributed to AlCl4. It has been
shown previously that in Lewis acidic melts there is an
equilibrium established between these two species according
to Scheme 1.20–23
Although the Al nucleus is relatively insensitive to
de-screening effects (compared, for example, to either 1H or 13C)
that are reflected in the value of chemical shift, d/ppm, these
assignments were based on line broadening phenomena that
originate in quadrupolar nuclei from mobility (free tumbling) and
symmetry differences. Subsequently when compared with
AlCl4, the Al2Cl7 species has a slower free tumbling rate
in the liquid (fast T2 relaxation time) and lower symmetry
(i.e. prolate). The AlCl4 species, on the other hand, is more
mobile (rapid free tumbling) with tetrahedral (pseudo spherical)
symmetry; these molecular properties give a relatively slow T2
relaxation time resulting in less line broadening.
In order to extract quantitative information from the
spectra we performed numerical curve fitting based on a very
simple procedure; we have assumed that each spectrum is a
linear combination of only two other spectra where each of
these corresponds to one of the two chloroaluminate species.
Each spectral line has associated with it a value of chemical
shift, d/ppm, peak width, s (half height full width HHFW =
s/ppm) and integral intensity. The latter of these values is
related to the total amount of the species present in the sample.
Using simple numerical iteration the values of these three
z 30% v/v toluene to ionic liquid corresponds to 18 wt%.
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Scheme 1
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Fig. 4 27Al spectra of (a) 1.5 : 1 AlCl3 : BIMIM neat liquid (sample 1):
experimental measured spectrum (black), fitted component 1,
d = 99.6 ppm (red), fitted component 2, d = 108.0 ppm (blue), linear
combination of fitted data (green); (b) 2.0 : 1 AlCl3 : BIMIM neat
liquid (sample 3): experimental measured spectrum (black), fitted
component 1, d = 109.0 ppm (blue), fitted component 2, d = 102.4 ppm
(red), linear combination of fitted data (green).
parameters were varied in such a way as to minimise the
difference between the linear sum of the two ‘‘model’’ spectra
and the measured data. The outcomes of two such procedures
are shown in Fig. 4. Corresponding data for a series of
experiments are summarised in Table 1.
In the first case, Table 1, sample 1 (also Fig. 4(a)), the fitted
parameters are presented for a sample of neat liquid having a
1.5 : 1 AlCl3 : BMIM composition. These show the positions
of the two peaks, 99.6 and 108.0 ppm, corresponding to the
AlCl4 and Al2Cl7 species, respectively. The line widths,
s/ppm, were measured directly from the spectra and the T2
relaxation times were calculated from s using eqn (1), where
f = f0/1  106 and f0 is the fundamental frequency for 27Al; in
this experiment f0 = 104.261 MHz.
The integral ratio, S, is calculated from the integrated
intensity ratio of the fitted peaks at 108.0 and 99.6 ppm,
respectively, giving a species ratio, Al2Cl7 : AlCl4, of
approximately 3 : 1. This is consistent with previous data on
Lewis acidic melts.20–22 The data shown in Table 1, sample 2,
correspond to the same sample with the addition of toluene
(23% v/v) as a diluent; the peak positions (ppm) remain very
similar, however, both of the fitted spectral lines are very much
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narrower reflecting greater mobility (faster tumbling rates)
that correlates with slower T2 relaxation. This is a consequence
of the lower viscosity. Additionally there is very much less
of the narrow line component and integration gives a value of
S = 0.101 corresponding to a ratio, Al2Cl7 : AlCl4, of
approximately 10 : 1.
1
T2 ¼ ð1Þ
fps
Hence the effect of the diluent is two fold: (i) the mobility of
both species is improved and this is evidenced by the increase
in spin–lattice relaxation time, T2; the largest effect is seen for
the most mobile species, AlCl4, where T2 increases from
3.82 ms to 6.68 ms; (ii) the equilibrium, Scheme 1, has also
been shifted to the right. Whilst the direction of this equili-
brium shift is counter intuitive it may be the case that the high
relative concentration of toluene has caused the liquid to
behave as a concentrated salt solution (rather than like an
ionic liquid). Here charge–charge interactions dominate and
ionic aggregation is favoured because of the low dielectric
constant of toluene. Also we have observed that the colour of
the liquid becomes darker with the addition of toluene
indicating the presence of a neutral charge-transfer complex
AlCl3(toluene). Formation of this complex may be favoured
by the increase in concentration of Al2Cl7 because the central
bridging Cl atom will be more labile and therefore more easily
displaced by the toluene ligand. What is clear from Table 1 is
that the speciation in the ionic liquid changes markedly when
toluene is added to the liquid in contrast to the potentiometry
results from Osteryoung and Robinson.19
The fitted 27Al NMR data for the more Lewis acidic liquids
(2.0 : 1 AlCl3 : BMIM composition) presented in Table 1 as
sample 3 and sample 4 show a slightly different picture. Here
the positions of the two spectral features are shifted, appearing
at d = 102.4 and d = 109.7 ppm. The first of these two shifts
may be more significant indicating a difference in speciation.
This is supported by the fact that both of the spectral lines are
very broad. This may indicate that AlCl4 is present only
in very small amounts and consequently the presence of
additional higher order aluminium containing oligomers (slow
tumbling, low symmetry) as is consistent with the increase in
Lewis acidity. The two spectral features are present in
approximately the same amounts i.e. S = 0.981. Upon
addition of toluene as diluent (sample 4) the peak positions
remain very similar and the integral ratio is almost unchanged,
S = 1.025. These observations indicate that the speciation in
the more acidic melt is less sensitive to perturbation by the
addition of diluent. The mobilities of both spectral com-
ponents, however, are increased as seen by the line narrowing.
This is most pronounced in the peak at d = 102 ppm.
Fitted data for the 3-month aged sample of liquid having
2.0 : 1 AlCl3 : BMIMCl composition are presented in Table 1
as sample 5. We have observed that Al plating from old
samples of liquid often leads to poor coatings. Also, that
further addition of AlCl3 can restore such aged liquids to a
condition where high quality adherent Al coatings can be plated.
We have attributed this effect to differences in speciation but
the data for sample 5 (Table 1) do not offer much in the way of
insight. The peak positions, spectral line widths and integral
Phys. Chem. Chem. Phys., 2010, 12, 1862–1872 | 1865
 Table 1 Chemical shift, line width and relaxation time data for 27Al NMR spectra of various AlCl3 : BMIM ionic liquids with and without the
addition of toluene
Chemical shift
Sample d/ppm
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(1) 1.5 : 1.0 99.6
AlCl3 : BMIM 108.0
liquid neat
(2) 1.5 : 1.0 99.5
AlCl3 : BMIM 106.5
liquid + 23% v/v toluene
(3) 2.0 : 1.0 102.4
AlCl3 : BMIM 109.0
liquid neat
(4) 2.0 : 1 103.6
AlCl3 : BMIM 109.7
liquid + 27% v/v toluene
(5) 2.0 : 1.0 102.8
AlCl3 : BMIM 111.3
liquid neat, 3 months old
intensities of the model data for the aged sample are very
similar to those of the neat freshly prepared liquid (sample 3)
and to the fresh liquid with added toluene. Furthermore,
addition of AlCl3 to this liquid does not change the NMR
spectrum appreciably even though the quality of coatings
obtained is restored to that approaching the freshly prepared
liquid. It is clear that these effects must be related to speciation
changes but it seems likely that line broadening effects together
with relative amounts of the different constituent species preclude
a meaningful analysis using the methods described here.
These are consistent with previous reports and show that in
the 2AlCl3 : 1BMIMCl mixture the major species was Al2Cl7.
It would not be expected for the addition of toluene to cause a
change in speciation and FAB-MS confirmed that the same
species are present although the signals for the individual
species do change their relative intensities. The data show that
the ratio of Al2Cl7 : AlCl4 is approximately constant for the
2AlCl3 : 1BMIMCl mixtures with and without the addition of
toluene. In the less acidic 1.5AlCl3 : 1BMIMCl mixture,
however, the amount of Al2Cl7 is considerably increased.
In this case the addition of toluene has a significant effect
which is to decrease still further the amount of Al2Cl7 in the
liquid. This could be explained by considering the equilibria,
shown in Scheme 2, that occur in the ionic liquids.
Another aspect of these speciation equilibria is that the
changes to ionic structure and populations could lead to
changes in conductivity. However, we have previously shown
that the charge carrier mobility in such liquids is often a
function of available free volume, rather than an intrinsic
property of the molecular ion. This actually makes correlations
between conductivity and speciation very difficult to interpret.
One effect of changing speciation is that the amount of
under-potential deposition (upd) will change as upd only
occurs with AlCl4. This can be seen qualitatively in Fig. 1
and 2(i) and (ii), where the charge for upd is decreased when
toluene is added to the liquid. To find the effect of toluene on
the growth rate, chronocoulometry of the systems shown in
Scheme 2
1866 | Phys. Chem. Chem. Phys., 2010, 12, 1862–1872
Line width
s/ppm T2/ms S
8.0 3.82
20.0 1.53 0.295
4.6 6.68
16.7 1.83 0.101
27.2 1.12
33.3 0.09 0.981
15.2 2.01
22.7 1.35 1.025
21.0 1.45
35.0 0.09 1.055
Fig. 1 was carried out and the results are shown in Fig. 5.y For
the potential step from +0.2 to 0.8 V, Fig. 5(a), the potential
was held at anodic limit for 1 minute prior to the potential
step. It can be seen that the rate of metal deposition is faster in
the liquid to which toluene has been added which would seem
logical given the voltammetry in Fig. 1. Numerous chrono-
amperometric investigations have studied the mechanism of
nucleation and found that it is close to the response for
instantaneous nucleation.11–13 The studies have, however,
stepped from a regime in which the electrode is already
covered in a monolayer of upd (under-potential deposited)
aluminium and hence these studies have looked at the deposition
of Al on upd Al. To determine the effect of upd Al on growth
rates the chronocoulometry experiment was repeated starting
at +1.4 V, Fig. 5(b). Under these conditions no charge flows
at the preconditioning step and when the potential is stepped
to 0.8 V the rates of growth of aluminium are approximately
the same irrespective of the addition of toluene.
This is the first evidence of the upd layer affecting the
morphology of the metal deposited on the electrode surface.
It could be questioned why toluene affects the rate of deposition
when upd occurs in both liquids. Close inspection of the
charge passed during the preconditioning step at 0.2 V reveals
that there is a difference in the rate at which upd material is
deposited and it is also evident from Fig. 1 that upd occurs
more readily when no toluene is added. The same results are
observed for the deposition of zinc from deep eutectic solvents
made up from choline chloride and urea and choline chloride
and ethylene glycol.23,24 In this case the upd is controlled by
the different speciation caused by the hydrogen bond donors.25
Chronopotentiometry experiments were carried out in both
the neat liquid and the one to which 18 wt% toluene had been
added. The experiments step the potential from a given value
to the open-circuit potential. Fig. 6 shows that the time taken
for the system to reach equilibrium i.e. for upd material to be
deposited, is considerably longer when toluene is added to the
y The absolute values of charge at long times are greater in Fig. 5(b)
than in Fig. 5(a), however, this may be, in part, due to surface area
effects as the electrode was removed, cleaned and polished between
experiments.
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Fig. 5 Chronocoulometry of the system shown in Fig. 2 for the
potential step from 0.2 to 0.8 V (a) and +1.4 to 0.8 V (b), with and
without added toluene as indicated.
liquid than when the neat liquid was used. This is particularly
marked for the falling transients where E > 1.0 V.
This has important ramifications for the experimental method
and the reproducibility of the experiments. When the electrode
is immersed in the solution upd will occur spontaneously. If an
anodic etch of the substrate is followed immediately by an
electrodeposition process then no upd can occur and nucleation
and growth will be different to a system in which upd occurs.
The length of time that an electrode is immersed in a solution
prior to deposition will also affect the extent of upd and hence
the way in which a metal grows. These parameters have
never before been considered in the deposition of metals from
ionic liquids.
The effect of upd can be easily and unequivocally demon-
strated. A steel electrode was immersed in a 1BMIMCl : 2AlCl3
ionic liquid in the absence of an applied potential for
10 minutes, allowing upd to occur. At the same time as the
deposition potential was applied an additional 5 ml of ionic
liquid was injected into the base of the cell ensuring that an
additional 1 cm of the electrode was coated. This portion of
the electrode had not been able to deposit upd aluminium but
had been exposed to the same deposition conditions as the rest
of the sample. An apparent difference could be observed in the
resulting sample in the two regions and the morphologies can
clearly be seen in the AFM images shown in Fig. 7. The crystal
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Fig. 6 Chronopotentiometry recorded at different preconditioning
potentials for (a) neat 2 : 1 acidic AlCl3 : [BMIM]Cl ionic liquid and
(b) with 18 wt% toluene.
size is considerably smaller in the sample where upd has not
occurred compared to that where it has. This is consistent
with the results obtained following the addition of toluene
where less upd occurred and smaller crystal/grain sizes were
observed. We infer from this that upd material coats the whole
surface and subsequent metal deposition is slow because
there are fewer growing centres than the corresponding
system without upd material. This would explain the chrono-
coulometry results observed in Fig. 5 and the resulting AFM
images in Fig. 7.
Fig. 8 shows SEM and optical images of a series of
aluminium deposits produced using 1BMIMCl : 2AlCl3 ionic
liquids without toluene, Fig. 8(a), and with toluene in varying
amounts, Fig. 8(b and c). It can be seen that the crystal/grain
size decreases when toluene is added, Fig. 8(b), and that
further increase in toluene concentration decreases the grain
size to such an extent that individual grains are no longer
discernable, Fig. 8(c). Fig. 8 also shows a photograph of the
samples and it can be seen that the progressive addition of
toluene changes the appearance of the deposit from dull grey
to a mirror finish. Clearly the addition of toluene also
increases mass transport which will sustain the rapid growth
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Fig. 7 AFM images of the deposits obtained from electrolysis at 1.0 V
of a 2 : 1 acidic ionic liquid (a) with no upd, (b) with upd and (c) with
the addition of 0.5 mol equivalent LiCl.
of the nuclei and prevent the needle-like growth observed by
others working with these systems.12,13
Effect of adding LiCl
The morphology of the deposit should also be affected by the
addition of species that affect the speciation and upd of metal
at the electrode surface. Endres et al. have recently used
pyridinium and imidazolium based bistriflimide ionic liquids
for the deposition of aluminium.14 These liquids result in
different deposit morphologies with pyridinium leading to
nano-structured metals and imidazolium yielding micro-
crystalline deposits. This was ascribed to a cation effect which
can only reasonably result from a difference in the double layer
structure. It is difficult to determine accurately from the
published results but the upd signal appears to be larger for
the imidazolium based liquid which would be consistent with
the above results.
To test the idea that the double layer structure affects upd
and changes material morphology an electrolyte with a small
cation should significantly affect nucleation and change
1868 | Phys. Chem. Chem. Phys., 2010, 12, 1862–1872
Fig. 8 SEM images (left) of aluminium deposited from (a) 1BMIMCl :
2AlCl3 without toluene at 1.0 V versus Al, (b) as (a) but with
25 wt% added toluene and (c) with 30 wt% toluene. Each SEM image
(left) is paired with the corresponding optical photograph of the same
sample (right).
deposit morphology. Fig. 1 shows the effect of adding 0.5 mole
equivalents of LiCl to the 1BMIMCl : 2AlCl3 ionic liquid. The
addition of LiCl appears to be the opposite of adding toluene
in that it encourages the growth of bulk material and
suppresses the growth of smaller nuclei. LiCl also promotes
the formation of upd aluminium. It is thought that the reason
for this could either be that the lithium cation acts as a strong
Lewis acid and promotes the dissociation of AlCl4 to AlCl3
close to the electrode surface or that the lithium cation is
preferentially present at the electrode surface and this
encourages the adsorption of AlCl4 at the electrode surface.
AFM data presented in Fig. 7(c) show that LiCl causes the
crystal/grain size of the Al deposit to be larger than that of the
pure liquid (either with or without added toluene, Fig. 7(a)
and (b)), which is in agreement with the voltammetric response
in Fig. 1 and confirms that peaks A and A 0 are due to small
particle size material whereas B and B 0 result from bulk Al
growth. The deposit thus obtained was charcoal grey in
appearance and exhibited poorer adhesion than that without
LiCl. This result appears to confirm the idea that the cation
could have an effect upon the deposition of aluminium,
however, the addition of LiCl also affects the Lewis acidity
of the liquid and this can be seen in the extent of upd observed
in Fig. 1. The addition of toluene to a system containing LiCl
also allows the deposition of mirror finish aluminium showing
that it is not the presence of Li+ alone that causes the
deposition of large particulate deposits. This does not disprove
the cation effect on deposit morphology but it highlights that
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 speciation and upd are also important factors in controlling
the nucleation and growth mechanism in ionic liquids.

Anode effects
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Bulk electrolysis was carried out of a 1 : 2 BMIMCl : AlCl3

ionic liquid at a constant potential of 1.0 V for 100 hours at
22 1C. Following this time the electrodes were washed, dried
and the change in mass determined. It was found that the
increase in cathodic mass (0.127 g) was very similar to the
decrease in anodic mass (0.130 g) and the overall current
efficiency was 97%. This shows that the anode is indeed
soluble. Visual inspection of the anode and cathode shows
that the morphology of the deposit was not even despite
the constant distance between the tubular anode and the
cylindrical cathode along the length of the sample. The
difference in deposit morphology on the anode and cathode
as a function of immersion depth can be seen in Fig. 9. Close
to the top of both electrodes smooth, bright deposits were
obtained whereas at the bottom of the cell the anode was
pitted and the cathode deposit was dendritic in morphology.
Pitting occurs due to uneven dissolution rates which charac-
teristically happen when an oxide layer is not completely
Fig. 9 SEM images of Al anode (a, c, e) and the corresponding
removed from a surface. We propose that a small amount of
cathode (b, d, f) morphologies as a function of immersion depth: (a, b)
hydrolysis of AlCl3 takes place close to the interface with the
2 mm, (c, d) 8 mm and (e, f) 17 mm.
nitrogen and the trace of HCl produced could remove the
aluminium oxide from the anode surface whereas at the base
of the cell oxide removal is slow. Repeating the experiment
with an anode that has not been able to repassivate leads to a
brighter and more even surface finish on the cathode. It can be
concluded therefore that the anodic process has a significant
role upon the morphology of the cathodic deposit.
To investigate this process further voltammetry and electro-
chemical impedance spectroscopy were carried out for the
deposition and stripping of aluminium from a chloroaluminate
liquid on an aluminium electrode.
Fig. 10 shows the cyclic voltammetry for a 1 mm diameter
Al disc electrode in a 1 : 2 BMIMCl : AlCl3 ionic liquid. It
should be noted that while the aluminium deposited on the
cathodic sweep is completely stripped on the anodic sweep the
underlying aluminium electrode material is not significantly
stripped on further anodic polarisation. The limiting anodic
current suggests a mass transport limited process which could
result either from slow migration of ions through an oxide film
or a slow dissolution of Al limited by the availability of
suitable ligands in the ionic liquid. It must be appreciated that
although the ionic liquid is made up from a high concentration
of BMIMCl the Lewis acidity of AlCl3 ensures that the Cl
activity is effectively zero. Hence Al(III) species must compete
with AlCl4 for the halide ligand.
Fig. 10 shows the effect of adding toluene on both the anodic
and cathodic voltammetric responses on an aluminium disc
electrode. It can be seen that the cathodic charge, Fig. 10(a), for
the deposition of aluminium is largely unaffected by the
addition of toluene and this is also reflected in the stripping Fig. 10 Cyclic voltammograms for a 1 mm diameter Al disc electrode
of the metal deposited on the cathodic sweep such that the in a 1 : 2 BMIMCl : AlCl3 ionic liquid with varying amounts of added
charges for these two processes are effectively identical. toluene: (a) cathodic potential regime and (b) anodic potential regime.
The effect of toluene does, however, have a significant effect Sweep rate = 20 mV s1. The inset to panel (b) shows consecutive first
upon the limiting current for the dissolution of the underlying and second scans of the same electrode in neat liquid.

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 aluminium substrate, Fig. 10(b). This suggests that mass
transport limits the rate of anodic dissolution and if electrodes
of equal area were used in an electrolysis experiment the
anodic reaction would control the rate of the overall deposition
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process. This is contrary to what would be expected for

aqueous plating solutions where the anodic process can
generally be ignored as it is usually considerably faster than
the cathodic process. This also explains the observation that
for many deposition experiments in ionic liquids the current
density is independent of the applied voltage.
Fig. 10 suggests that a passive oxide film is present on the
electrode surface but this dissolves slowly on polarisation to
increasingly anodic potentials. A second scan from 0.5 to 2.0 V
produces a flat response showing that the oxide has all been
removed, Fig. 10(b) see inset. The limiting current does not
decrease on cathodic polarisation showing that the oxide does
not reform. When toluene is added to the liquid the limiting
current increases due to two factors: a decrease in the overall
viscosity of the liquid and an increase in the concentration of
chloride ions in solution.9 Electrochemical impedance spectro-
scopy (not shown) confirms the presence of the oxide film at
potentials below 1.5 V. At 1.5 V two semi-circular responses
are observed in the Nyquist plot and at 2 V a mass transport
limited process dominates the Nyquist plot. The same is
observed when the potential is returned to 0.5 V without
repolishing the electrode. This confirms the proposed mecha-
nism of slow oxide dissolution followed by a dissolution of
aluminium limited by the diffusion of a suitable ligand to the
electrode surface.
Fig. 11 Cyclic voltammogram for a 1 mm diameter Al disc electrode
The experiment, Fig. 10, was duplicated and Fig. 11 shows a
in a 1 : 2 and 1 : 1.5 BMIMCl : AlCl3 ionic liquid as indicated;
voltammogram for the 1 : 2 BMIMCl : AlCl3 ionic liquid
(a) cathodic potential regime and (b) anodic potential regime. The
compared with the same experiment for the corresponding potential sweep rate fixed at 20 mV s1.
1 : 1.5 BMIMCl : AlCl3 ionic liquid. The anodic current no
longer reaches a limiting value but continues to climb even on
the cathodic cycle.
This is because the aluminium is pitted and the overall
current increases due to the increased surface area. The rapid Scheme 3
dissolution of the aluminium is not due solely to the viscosity
of the liquid since the 1 : 1.5 liquid is considerably more aluminium. What is surprising is that in the absence of toluene
viscous than the 1 : 2 liquid. This can be explained using the the limiting current for copper dissolution is half that for
AlCl4/Al2Cl7 data shown in Table 1. The equilibrium in aluminium; this could be explained in view of the fact that
Scheme 3 will lie over to the right and the aluminium will copper is less Lewis acidic than aluminium.
dissolve more rapidly. Impedance spectroscopy confirms that Therefore the equilibrium shown in Scheme 4 will favour the
in both cases the oxide is present below 1.5 V. Above this value right hand side to a lesser extent than that shown in Scheme 3.
it dissolves slowly and at 2.5 V a diffusion limited process The addition of 14.5 wt% toluene, however, causes a 10 fold
controls the rate of metal dissolution. These results show that increase in the limiting current for the dissolution of copper
both the presence of a metal oxide and the availability of a compared to aluminium. Liao and Hussey25 measured the
ligand to solvate the dissolving aluminium ion are important viscosity for the EMIMCl : AlCl3–benzene system and found
in the dissolution rate. Bulk deposition of aluminium from the that the neat 1 : 2 mixture had a viscosity of 13.7 cP. The
1 : 2 ionic liquid led to a dull deposit whereas deposition from addition of 15 wt% toluene reduced the viscosity to 7.08 cP
the 1 : 1.5 at the same applied potential (1.0 V) led to a bright and the addition of 30 wt% decreased it to 4.00 cP. The ratio
surface. This is surprising given that the 1 : 1.5 liquid is more of viscosities, while accounting for the trends observed in
viscous and clearly has less aluminium. Fig. 10 and 12, does not account for the ratio of limiting
To monitor the effect of the oxide layer and diffusion the currents. The viscosity of the 1 : 1.5 liquid (16.14 cP) certainly
above experiment was repeated using a copper electrode of the does not explain the anodic current observed in Fig. 11.
same size as the aluminium one used above. It can be seen An alternative method of increasing the rate of the anodic
from Fig. 12 that the oxidation potential of the copper is process is to immerse the electrochemical cell in an ultrasonic
less positive than that of the aluminium (cf. Fig. 11) which bath. Fig. 13 shows that both the cathodic and anodic currents
would be expected given the presence of the oxide layer on are increased by a factor of 10 under ultrasonic conditions.

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Fig. 12 Cyclic voltammogram for a 1 mm diameter Al disc electrode
in a (a) 1 : 2 and (b) 1 : 1.5 BMIMCl : AlCl3 ionic liquid. Sweep
rate = 20 mV s1.
Scheme 4
Current densities of ca. 40–50 mA cm2 could be achieved at
ambient temperature, which were approximately 5 times
those observed using the same conditions in a silent system.
This means that aluminium can be deposited at rates that
are comparable with other metals deposited from aqueous
solutions.
Conclusion
We have shown that the addition of both toluene and LiCl to a
chloroaluminate based ionic liquid affects the morphology of
the aluminium electrodeposited from it. Toluene changes the
speciation of aluminium complexes in the liquid and hence
the extent of upd on the electrode surface. We have shown for
the first time that upd affects the rate of metal growth on the
electrode surface. Voltammetry and AFM have shown that
aluminium grows with two different morphologies depending
on the applied potential. The mechanism behind this is as yet
unknown but it is clear that metal growth from ionic liquids
depends upon a complex mixture of speciation and mass
transport issues. Other recent studies in (trifluoromethylsulfonyl)-
amide based chloroaluminate liquids26,27 have also shown that
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c the Owner Societies 2010
Fig. 13 Cyclic voltammogram for a 1 mm diameter Al disc electrode
in a 1 : 1.5 BMIMCl : AlCl3 ionic liquid and the effect using
ultrasound. Sweep rate = 10 mV s1.
liquid properties and subsequently Al deposition can be
strongly influenced by Al speciation. However, a detailed
investigation by Endres et al.28 has shown that cation effects
and surface interactions in the interfacial solvation layer can
be dominant where changes in bulk speciation equilibria are
quite subtle. Some of these aspects are described in another
manuscript in this themed issue.
Here we also conclude that, unlike most aqueous deposition
processes, the anodic behaviour of aluminium in Lewis acidic
chloroaluminate liquids can control the rate of deposition. The
anodic process is dependent not only upon the viscosity of the
liquid, but also upon the relative concentrations of Cl,
AlCl4 and Al2Cl7. In order to elucidate the speciation and
the position of the speciation equilibria we will shortly engage
in the study of Raman data from these systems.
Experimental section
Aluminium chloride (Aldrich >99%) and n-butyl methyl
imidazolium chloride (BMIMCl) (Aldrich >99%) were dried
under vacuum on a Schlenk line for 2 h prior to use. The ionic
liquids were formed by stirring the two components together
at 20 1C until a homogeneous, straw brown liquid formed. The
liquids were maintained under a dry nitrogen atmosphere at all
times. Voltammetry was carried out using an Autolab
PGSTAT12 potentiostat controlled with GPES software. A
three-electrode system consisting of a platinum disc working
electrode (0.5 mm radius), sealed in glass, a platinum counter
electrode and an aluminium wire reference electrode was used.
The working electrode was polished with 0.3 mm alumina
paste, rinsed and dried prior to all measurements. All voltammo-
grams were performed at 20 1C and a scan rate of 50 mV s1.
Electroplating experiments were carried out using two
electrodes set up under N2 atmosphere in a Schlenk tube.
The cathodes were mild steel rods with a diameter of 0.6 cm,
and the anode was a cylinder of Al with a diameter of 1.6 cm
placed around the cathode. The cathodes were cleaned using
P400 sand paper followed by rinsing with deionised water,
then dipped into 5 wt% HCl, acetone and dichloromethane for
Phys. Chem. Chem. Phys., 2010, 12, 1862–1872 | 1871
 5 min, respectively, before transferring into a Schlenk tube.
The anode was cleaned by dipping into 1% HNO3, 65%
H3PO4, 5% acetate acid and water for 5 min, and then rinsed
with deionised water and acetone. Anodic etching of mild steel
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rods was performed by applying +1 V for 30 s to remove any
possible oxide layer. All samples were prepared by applying
constant potentials for 60 min. Samples were rinsed using
toluene followed by isopropanol and then deionised water.
Surface analysis was carried out using scanning electron
microscopy (Philips XL30 ESEM) and energy dispersive
analysis by X-rays (EDX). AFM images were acquired using
a Digital Instruments (DI) Nanoscope IV, Dimension 3100
(Veeco) instrument using either resonant (tapping) or contact
mode (software version 6.12).
Acknowledgements
The authors would like to thank Dr Gerry Griffith (University
of Leicester) for helpful discussion and acknowledge the EU
under the FP6 programme for funding this work through the
IONMET project (wwww.ionmet.eu). Dr Abood would like to
acknowledge both CARA and SRF for fellowship funding.
Notes and references
1 A. P. Abbott and K. J. McKenzie, Phys. Chem. Chem. Phys., 2006,
8, 4265–4279.
2 F. Endres, ChemPhysChem, 2002, 3, 144.
3 Electrochemical Aspects of Ionic Liquids, ed. H. Ohno, John Wiley
& Sons, New York, 2005.
4 F. Endres and S. Zein El Abedin, Phys. Chem. Chem. Phys., 2006,
8, 2101.
5 G. E. McManis, A. N. Fletcher, D. E. Bliss and M. H. Miles,
J. Electroanal. Chem., 1985, 190, 171.
6 F. H. Hurley and T. P. Wier, J. Electrochem. Soc., 1951, 98, 207.
1872 | Phys. Chem. Chem. Phys., 2010, 12, 1862–1872
7 W. H. Safranek, W. C. Schickner and C. L. Fraust, J. Electrochem.
Soc., 1952, 99, 53.
8 R. A. Osteryoung and J. Robinson, J. Am. Chem. Soc., 1979, 101,
323.
9 Y. Zhao and T. J. VanderNoot, Electrochim. Acta, 1997, 42, 3.
10 Q. X. Liu, S. Zein El Abedin and F. Endres, Surf. Coat. Technol.,
2006, 201, 1352–1356.
11 Y. Zhao and T. J. VanderNoot, Electrochim. Acta, 1997, 42,
1639–1643.
12 T. Jiang, M. J. Chollier Brym, G. Dube, A. Lasia and
G. M. Brisard, Surf. Coat. Technol., 2006, 201, 10–18.
13 T. Jiang, M. J. Chollier Brym, G. Dube, A. Lasia and
G. M. Brisard, Surf. Coat. Technol., 2006, 201, 1–9.
14 S. Zein El Abedin, E. M. Moustafa, R. Hempelmann, H. Natter
and F. Endres, ChemPhysChem, 2006, 7, 1535–1543.
15 W. H. Safranek, W. C. Schickner and C. L. Fraust, J. Electrochem.
Soc., 1952, 99, 53.
16 E. Peled and E. Gileadi, J. Electrochem. Soc., 1976, 123, 15.
17 (a) Q. Zhu, C. L. Hussey and G. R. Stafford, J. Electrochem. Soc.,
2001, 148, C88; (b) Q. Liao, W. R. Pitner, G. Steward and
C. L. Hussey, J. Electrochem. Soc., 1997, 144, 936.
18 W. R. Pitner, C. L. Hussey and G. R. Stafford, J. Electrochem.
Soc., 1996, 143, 130.
19 R. A. Osteryoung and J. Robinson, J. Electrochem. Soc., 1980,
127, 122.
20 A. P. Abbott, C. A. Eardley, N. R. S. Farley, G. A. Griffith and
A. Pratt, J. Appl. Electrochem., 2001, 31, 1345; J. S. Wilkes,
J. S. Frye and G. F. Reynolds, Inorg. Chem., 1983, 22, 3870.
21 L. Heerman and W. D’Olieslager, Inorg. Chem., 1985, 24, 4704.
22 R. J. Gale and R. A. Osteryoung, Inorg. Chem., 1979, 18, 1603.
23 A. P. Abbott, J. C. Barron and K. Ryder, Trans. Inst. Met. Finish.,
2009, 87, 201.
24 A. P. Abbott, G. Capper, K. J. McKenzie and K. S. Ryder,
J. Electroanal. Chem., 2007, 599, 288.
25 Q. Liao and C. L. Hussey, J. Chem. Eng. Data, 1996, 41, 1126.
26 P. Eiden, Q. X. Liu, S. Zein El Abedin, F. Endres and I. Krossing,
Chem.–Eur. J., 2009, 15, 3426.
27 N. M. Rocher, E. I. Izgorodina, T. Ruther, M. Forsyth,
D. MacFarlane, T. Rodopoulos, M. D. Horne and A. M. Bond,
Chem.–Eur. J., 2009, 15, 3435.
28 R. Atkin, S. Zein El Abedin, R. Hayes, L. H. S. Gasparotto,
N. Borisenko and F. Endres, J. Phys. Chem. C, 2009, 113, 13266.
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