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Processing of metals and metal oxides using ionic liquids

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Andrew P. Abbott, Gero Frisch,* Jennifer Hartley and Karl S. Ryder

Received 20th October 2010, Accepted 4th January 2011
DOI: 10.1039/c0gc00716a
Hydrometallurgy lies at the heart of many industrial processes and is the source of a large volume of
aqueous waste. Treating dilute streams of acidic and basic by-products is both energy and chemical
intensive, and is one of the largest sources of metal-based emissions into the environment. Over the
past decade, numerous studies have been made into the use of ionic liquids for metal dissolution,
extraction and recovery. This article critically reviews the potential efcacy of these methods and
signposts the areas where further research is needed.

Aqueous metal processing

The processing and reprocessing of metals is probably one the
largest sources of low-grade waste and one of the largest users
of energy of any industrial sector. Most processes are based on
either high temperature or hydrometallurgical methodologies
and a schematic diagram of the relevant steps is shown in Fig. 1.
Metal processing is naturally complex due to the diverse sources
of starting materials e.g. metals, oxides, suldes, carbonates,
phosphates, silicates and complex slags, sludges and alloys.
Metal oxides are insoluble in most molecular solvents so the
solution based processing of metals is done in either melts or
very acidic or basic conditions. Both methods have considerable
disadvantages regarding energy demand and waste. As Fig. 1
shows, there are numerous steps involved in the extraction and
recycling of metals. The methodology adopted depends upon the
original matrix, the required purity and value of the end product.

Fig. 1 Schematic diagram of the steps involved in metal extraction and

recovery.

It is a common misconception that water is a green solvent

not least since the major constituent must ultimately return at

Department of Chemistry, University of Leicester, Leicester, LE1 7RH,

UK

This journal is The Royal Society of Chemistry 2011

some point to the watercourse. Hydrometallurgy has its origins

at the end of the 19th century with the cyanide extraction of
gold and the basic extraction of bauxite.1 The environmental
impact of these technologies is a well documented issue and is a
serious legacy for future generations.2,3 In processes which follow
modern standards for environmental protection, all solutes must
be removed before the solvent is discharged to the environment. Especially heavy metals must be removed to extremely
low concentrations which can be chemically and energetically
intensive. Solutions have to be neutralised before disposal and
salt discharge can be an issue. In general hydrometallurgy is used
for more complex mixtures with lower process volumes due to
improved capital and labour considerations.4
There are four main methods to recover metals from solution;
precipitation, ion exchange, electrodeposition and cementation.
Precipitation usually adjusts the pH or adds a chemical precipitant and occulent. Metals are often precipitated as hydroxides,
suldes, or carbonates and the solubilities of the metals in
solution will decide the process used.
Electrowinning metals from aqueous systems is an efcient
and the most commonly used recovery technology for metals
with positive redox potentials such as gold, silver and copper,
it does not work as well on others, such as chromium and is
impossible for metals such as aluminium. The electrodeposition
process is usually sensitive to parameters like pH which must
be accurately maintained to control the deposition process. This
is a well studied area and pH-potential (Pourbaix) diagrams
exist for most systems.5 Complexing agents such as cyanide or
ammonia can be used to adjust metal speciation and thus control
solubility and deposition properties of both, the main solute and
impurities.6 If there is an over potential in water, hydrogen gas
can evolve at the cathode and oxygen at the anode. This can also
lead to embrittlement of the metal deposit, diminish its quality
and lead to low current efciency.
Most base metals like aluminium or chromium have to be
chemically or electrochemically reduced in high temperature
processes often after an aqueous pre-treatment of the ore. Most
of these procedures have extremely high energy demands and
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sometimes produces large volumes of aqueous waste. A modern

green metal processing technique will therefore have to take
place at moderate temperatures in a non-aqueous environment
which allows control of metal speciation, tolerates impurities
and at the same time exhibits suitable solubilities and current
efciencies.

Table 1 A selection of cations and anions used to make ionic liquids

for metal processing
Common cations

Discrete anions

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Ionic liquids
Due to their ionic nature metal oxides predominantly form
charged species upon dissolution and are therefore more soluble
in polar or ionic uids. High temperature molten salts at ca.
500 to 1000 C have been utilized to electrowin metals like Li,
Na, Ti and Al, which are inaccessible from aqueous media.7,8,9
High temperature molten salts being both ionic and aprotic
are highly suitable for electrowinning metals. They have high
conductivities, wide potential windows, low viscosities and high
solubilities for metal salts. Molten salts have the solvating power
of aqueous media, while not having detrimental properties
like hydrogen evolution. The issue with electrowinning from
molten salts is clearly the high temperature of operation and
the associated energy demand as well as practical issues such as
substrate specicity and material compatibility.
Ionic liquids as a low temperature alternative are currently
a popular area of research. Ionic liquids are systems with
an anionic and a cationic component which are liquid below
100 C.10 The denition is used to distinguish these uids from
high temperature molten salts but is completely arbitrary. Ionic
liquids have been of great interest resulting from useful physical
properties, yet negating the difculties of high temperature high
temperature molten salts. A variety of cations and anions are
described in the literature but for the application of metal
processing only a relatively small pallet of ionic liquids has been
used. These are shown in Table 1. The possibility to choose a
possible ligand as the anionic component allows control of the
speciation and thus chemical properties of metal solutes to a
much greater extent than in aqueous media since extremely high
activities of the ligands can be achieved.
Ionic liquids have clearly been reported to be green solvents
most notably for their low vapour pressure compared to
molecular alternatives. In the application of ionic liquids to
metal processing the green credentials of this methodology could
also come from a signicant reduction in the volume of low
level aqueous streams that would need to be processed and in
process intensication that could be brought about by improved
extraction efciency in biphasic processes. Today, it is generally
recognised that this is only part of the picture since many ionic
liquids do have signicant toxicity. Some ionic liquids have been
designed to contain ions which are known to have lower toxicity
and these include functionalised imidazoles,11 lactams,12 amino
acids13 and choline14 although it is only the last of these which
have been extensively applied to metal processing.

Eutectic ionic liquids

One of the key breakthroughs in the development of ionic liquids
came with the synthesis of a 1 mol. eq. N-ethylpyridinium
bromide : 2 AlCl3 by Hurley and Wier in 195115 which was a
eutectic liquid at 20 C. This was used for the electrodeposition
472 | Green Chem., 2011, 13, 471481

of aluminium16 and therefore sparked a large amount of research

for metal deposition. Using molecular orbital theory, Wilkes
and co-workers17 developed an ionic liquid, AlCl3 : 1-ethyl3-methyl-imidazolium, which had a room-temperature liquid
range between 33 and 67 mol% AlCl3 . In addition these rst
generation ionic liquids had a signicantly lower viscosity than
the corresponding pyridinium liquids and it is the imidazolium
cation that still dominates the ionic liquid literature. The term
rst generation is widely used throughout the literature but
is not particularly helpful. It tends to be used exclusively for
chloroaluminate systems but could equally well be used for
a system that forms an anion through interaction between a
Lewis acid and Lewis base. In our opinion a eutectic-based
ionic liquid is a more useful description of these systems. The
main limitation for chloroaluminate liquids is that they are
very moisture sensitive. Other eutectics are based on more
stable metal chlorides like ZnCl2 , however, this also increases
the viscosity.18,19 Eutectic liquids have also been synthesised
including SnCl2 and FeCl3 20 and these have been extended to
metal hydrate systems e.g. CrCl3 6H2 O.21
When extracting metals it is clearly undesirable to have a
high concentration of other metals already in solution and so
eutectic based ionic liquids have not been used extensively in the
realm of metal extraction. A variant of these metal-containing
eutectics has been developed by Abbott et al. using Brnsted
acids in place of the Lewis acids. The eutectics formed between
a quaternary ammonium halide and a hydrogen bond donor
such as alcohols, amides or carboxylic acids14,22 have advantages
for metal extraction in that they are simple to prepare, water
insensitive (although water miscible) and offer high solubilities
for many metal oxides at very low cost.23 These deep eutectic
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solvents are the rst to have been tested on a large scale for
digestion and metal recovery.24

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Ionic liquids with discrete anions

Discrete anion or second generation ionic liquids are composed of simple anions, as opposed to a mixture of anions
in equilibrium. Their discovery is ascribed to Wilkes and
Zaworotko who produced 1-ethyl-3-methylimidazolium tetrauoroborate and acetate for the rst time.25 It is this class of ionic
liquid which has dominated the literature ever since. The trends
in ionic liquid usage can be seen graphically in Fig. 2 which
shows the papers published on ionic liquids in given years with
specic anions. It can be seen that despite the water sensitivity
BF4 - and PF6 - are still the most commonly used anions.
The liquids used for extraction have tended to follow trends
in commercial availability and improved physical properties.
Anions such as BF4 - and PF6 - were initially used because of
their wide potential window,26,27 however, they were found to
slowly hydrolyse yielding HF,28 and liquids with more hydrophobic anions such as tri-uoromethanesulfonate [CF3 SO3 - ] and
bis-triuoromethanesulfonylimide [(CF3 SO2 )2 N- ] have become
popular recently.29 The potential window of these liquids can
be extremely large making it possible to electrowin more
reactive metals.30 The hydrolysis of uorinated anions however,
must not be overlooked in metal processing. Besides obvious
environmental and safety issues and corrosion of electrodes and
reaction vessels, uoride acts as a strong ligand for many metals
and can signicantly change metal speciation during a recovery
process.

as possible. The purity of these chemicals should be kept to a

maximum: due to their non volatile and viscous nature, it is
difcult for most of these liquids to be puried.
An important consideration when selecting an ionic liquid is
the viscosity and melting point of the liquid. This is largely
controlled by the cation and it has been shown that alkyl
substituents in the range C2 to C4 on an imidazolium or
pyridinium ring lead to the optimum uidity.32
In contrast, the anion has a more controlling effect on the
chemistry of the system since it interacts with the generally more
Lewis acidic metal solute. The complexation of the metal with
the anion controls speciation and thus all aspects of reactivity,
solubility etc. Anion effects on speciation are poorly understood.
Fig. 3 shows CuCl2 2H2 O dissolved in a variety of ionic liquids.
It is clear that the different anions and complexing agents present
in the liquids change the speciation of copper and this will clearly
affect the reactivity. The subsequent effects on redox potentials
are hard to quantify due to the ubiquitous issue of liquid junction
potentials. However, it is clear that reactivity can in principle be
controlled through judicious choice of the anion.

Fig. 3 Solutions of CuCl2 2H2 O in eight different ionic liquid

environments.

Fig. 2 Papers published on ionic liquids with given anions.

Ionic liquids are mostly made from a metathesis reaction of

a halide salt with, for example, a silver, group 1 metal or ammonium salt of the desired anion and acidbase neutralization
reactions.31 The ammonium or phosphorus salts are produced
from a quarternisation reaction between amine/phosphane with
a halogenated alkyl chain. Second generation ionic liquids can be
formed just from the rst step, e.g. the quarternisation reaction
between 1-ethyl-3-methylimidazole and methyl triate to give
[C4 mim][CF3 SO3 ].29 In most cases synthesis needs to occur in
an air and moisture free environment at as low a temperature
This journal is The Royal Society of Chemistry 2011

In order to be useful for electrochemical processes, ionic

liquids need to be good at dissolving metal salts. The high
solubility of metal salts in ionic liquids generally results from
the high concentration of anions. The solubilities of a range of
metals have been previously reviewed.33,34 On the other hand
Branco et al. studied the solubility of LiCl, HgCl2 and LaCl3
in several ionic liquids and found that the solubility constants
were relatively independent of the anion or cation for a series of
imidazolium tetrauoroborates and hexauorophosphates.35
Although this may seem unexpected in an ionic environment
it must be considered that second generation ionic liquids
often contain weakly coordinating anions and thus have similar
solvation properties. The solubility of these discrete anion ionic
liquids can be improved by introducing halides to the system or
by making the cation task specic. Functional groups added to
the cation can improve solubility of metal salts. An example of
these task specic ionic liquids (TSIL) is the addition of thioether
and thiourea groups to the side chain of the imidazolium cations,
thus making Hg2+ and Cd2+ ions soluble in the ionic liquids
phase.36 TSILs are discussed in greater detail below.
When processing metals the conductivity of the medium is
important as the metals are often recovered electrochemically.
Conductivity of an electrolyte is not only dependent upon the
number of charge carriers, but also upon their mobility. Ionic
liquids although they have a large concentration of charge
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carriers have lower than expected conductivities due to their

viscous nature. The conductivity and viscosity of ionic liquids
are summarised in a number of books and have successfully been
modelled using hole theory.37

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Ionic liquids in metal processing

Ionic liquids have been applied to most of the processes shown
in Fig. 1 although by far the most work has been carried out
in the eld of extraction. The reason for this is clearly due to
the practicality of using ionic liquids on a large scale. Metal
solubilities are unlikely to exceed 10% meaning at least a 10 fold
excess of solvent (and more typically 100 fold) is required even
for relatively soluble salts. Physical losses and mutual solubilities
with water will limit the choice of ionic liquids which can be
used. Physical losses from digestion are large due to adsorption
on the matrix. It is therefore likely that only high value metals
will be extracted by this procedure particularly using second
generation liquids. The high cost and viscosity of these liquids
means that they are better suited to small volume applications
and the prospect of concentrating metals from large volumes of
dilute aqueous solution into small volumes of ionic liquids is
clearly benecial.
Digestion of oxides
Hydrometallurgical digestion is carried out using various,
sometimes concentrated acids or bases such as sulfuric acid or
ammonia. Very little work has however been done for digestion
in ionic liquids due to the high cost of the solvent and the large
volume that would be required. The rst study of metal oxide
digestion was by Dai et al.38 who investigated the dissolution of
UO3 in imidazolium chloroaluminate melts. The solubility was
found to be in the range 1.52.5 10-2 mol dm-3 in Lewis basic
melts and the main metallic species in solution was found to
be [UO2 Cl4 ]2- . The solvation of uranium and europium ions in
these liquids has been modelled by Chaumont and Wipff.39 While
with hindsight this may not seem a suitable liquid for digestion
given its water sensitivity and high metal ion concentration the
importance of this work should not be underestimated as it set
the seed for all of the subsequent novel solvatometallurgical
processes. Huang et al. studied the recovery of nano-scale zinc
particles from phosphor ashes using an imidazolium PF6 salt
and this represented the rst study of digestion from a complex
matrix using ionic liquids with discrete anions.40
One of the major issues associated with digestion is the
solubility of metals and metal oxides in ionic liquids. Very little
work has been carried out into the factors controlling solubility
due primarily to the lack of consistent data in one ionic liquid
with a given series of comparable solutes. Future research would
have to investigate the effect of metal speciation and the addition
of oxide-binding reagents on the solubility and kinetics of the
dissolutions process.
Abbott et al. have carried out extensive studies on the
solubility of metal oxides in a variety of deep eutectic solvents.
The mixtures have been shown to have similar solvent properties
to ionic liquids with discrete anions41 but clearly have the
advantage that they are easier to produce on a large scale which
has obvious implications for metal recovery processes. Ligands
474 | Green Chem., 2011, 13, 471481

such as urea, thiourea or oxalate are well known complexants

for a variety of metals and can be made part of the ionic liquid.
It has been shown that these types of ionic liquids can dissolve a
range of metal oxides23 and they can be used to separate metals
from a complex mixture using electrochemistry.42 These liquids
are however all totally miscible with water and cannot be used
for biphasic extraction. The solubility of 17 metal oxides in the
elemental mass series Ti through Zn was reported in 3 ionic
liquids based on choline chloride.43 Selected data are shown in
Fig. 4. Judicious choice of the hydrogen bond donor can lead to
selectivity for extracting certain metals from complex matrices.22

Fig. 4 Solubility of metal oxides in a variety of DESs and HCl.

Classical solubility models are difcult to apply to these

kind of processes due to the lack of data on the species
formed. Speciation is a complex issue which depends largely
on the Lewis acidity of the metal and the Lewis basicity of possible ligands available in the ionic liquid. Several
techniques have been used to determine the species formed
and these have largely centred on EXAFS, Raman, FABMS and UV-vis spectroscopy. The modicum of work that
has been carried out is covered in two extensive reviews.44,45
The increasing use of bis(triuoromethylsulfonyl)amide based
ionic liquids for digestion and electrochemistry has led to
a concerted effort to investigate the complexation occurring
with these apparently weak ligands. A combination of EXAFS, Raman spectroscopy, X-ray crystallography and NMR
has been used and reports have described unexpected complexes. The dissolution of high concentrations of AlCl3 in 1butyl-1-methylpyrrolidinium bis(triuoromethylsulfonyl)amide
is thought to result in either [AlCl3 (NTf2 )]- or [AlCl2 (NTf2 )2 ]- .46
The dissolution of europium and yttrium oxides in betainium bis(triuoromethylsulfonyl)imide ([Hbet][Tf2 N]) resulted in the dissociation into the monomeric species
[Eu2 (bet)8 (H2 O)4 ][Tf2 N]6 , [Eu2 (bet)8 (H2 O)2 ][Tf2 N]6 2H2 O and
[Y2 (bet)6 (H2 O)4 ][Tf2 N]6 . Oxide is either protonated or substituted by the anionic component of the solvent.47 Similar studies by the same group investigated the dissolution of uranium oxide in 1-butyl-3-methylimidazolium
bis(triuoromethylsulfonyl)imide and results suggested the existence of [UO2 (NO3 )3 ]- i.e. for these highly charged ions oxide
was still bound to the metal centre which should be expected.48
Solvation in ionic liquids is poorly understood primarily
because of the complexity of the interactions between the solute
and the ionic components. A review by Kabrac has attempted
to express the links between liquid structure, dynamics and
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Table 2 Ligands commonly used in biphasic extraction studies using ionic liquids

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P(nBu)3

64, 65, 66

67, 68

69, 70

71

72, 73

74

solvation.49 Polarity parameters have been measured for ionic

liquids50,51 and these have been shown to be good at predicting
the kinetics of reactions in ionic liquids where hydrogen bonding
interactions dominate.52 However, these parameters are not an
accurate measure of Lewis acidity and basicity and so are less
informative for metal oxide solubility. It would be helpful if
new comparable parametric scales could be developed for this
purpose. These may also help with the denition of pH in ionic
liquids.
Digestion of metals
In aqueous solutions the oxidation of metals from their elemental state is usually carried out using oxidising acids such
as sulfuric acid, nitric acid or aqua regia. Different scenarios
need to be developed for ionic liquids because decomposition
of the ionic liquid is not usually a viable option. Work by
Whitehead et al. studied the recovery of gold and silver from
an ore sample using 1-butyl-3-methyl-imidazolium hydrogen
sulfate with iron(III) sulfate as the oxidant and thiourea as a
complexing agent. Relatively high yields of gold (>85%) and
silver (>60%) were obtained at room temperature although it
was relatively slow. The extraction process was relatively selective
over other metals in the ore (including Cu, Zn, Pb, Fe). The
results were comparable with the analogous sulfuric acid system
and an additional benet was that recycling of the ionic liquid
could be achieved. This was followed up by similar studies
investigating the effect of adding water and then varying the
sulde complexing agent and the anion of the ionic liquid. Gold
recovery was in excess of 85% from the ore samples tested and
silver recovery was in excess of 60% which was considerably
better than aqueous solutions.53,54
In our recent work,55 we have used iodine as a stable, reversible
electrocatalyst for the dissolution of a range of metals. It was
shown that the redox potential of I2 /I- was more positive
than that of most common metals and could even be used
for the oxidation and recovery of gold. It was also used for
the electrocatalytic dissolution of copper/zinc mixtures and it
This journal is The Royal Society of Chemistry 2011

was shown that copper could be quantitatively separated by

electrodeposition.
Extraction. Non-aqueous solvents have a long history in
metal processing and the general aim is to use an immiscible
organic solvent containing a complexing agent to extract the
metal from an aqueous solution.56 The discovery of water
immiscible ionic liquids naturally suggested their use for biphasic
metal extraction. This was the rst area of metal processing to
which ionic liquids were applied and remains the most widely
studied. It is, however, not just as a simple replacement for
organic solvents that ionic liquids have been applied. Most of
the studies have used classical non-aqueous ligands dissolved in
a variety of liquids to investigate the partition of metals.
The majority of studies have used salts with imidazolium
cations and several have focused on uranium processing. Rogers
et al. were the rst to recognise that ionic liquids with discrete
anions could be used for biphasic extraction processes and
they found partition coefcients similar to molecular biphasic
systems.57 Ionic liquids have been used for the extraction of
neutral organic solutes58,59 and biomolecules60 and these have
been reviewed recently.61,62,63 Numerous studies have focused on
metal ion extraction. These can be split into three main methodologies; the use of classical, neutral ligands to complex metal
ions, selective extraction of metals through anion interaction and
task specic ionic liquids. Table 2 shows a selection of neutral
ligands and ionic liquids that have been used to extract metals
from aqueous solutions.
Amongst the earliest studies was that of Dai et al.75 who
used crown ethers and calixarenes to extract a range of metals
from aqueous solutions. The work showed that large distribution
coefcients could be achieved using ionic liquids in preference
to organic solvents. Studies by Rogers et al. used azonaphthols
and crown ethers76 in a similar manner.
The mechanism of metal extraction is important as it governs
the viability of the process. The efcient extraction of the metals
can only be achieved if the ionic liquid or one of its components
does not leach out during the extraction process. Charged
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Table 3 Task specic ionic liquids used for metal extraction

TSIL

Metal

(CH3 )3 N+ CH2 COO-

Sc2 O3 , Y2 O3 , La2 O3 , Pr6 O11 , Nd2 O3 , Sm2 O3 , Eu2 O3 , Gd2 O3 , Tb4 O7 , Dy2 O3 , Ho2 O3 , 89, 90
Er2 O3 , Tm2 O3 , Yb2 O3 , Lu2 O3 , UO3 , PbO, ZnO, CdO, HgO, CuO, Ag2 O, NiO, PdO
Hg2+ , Cd2+
93

Am3+

94

Zn2+ , Cd2+ , Hg2+ , Tl+ , Pb2+ , Sn4+ , Ba2+

95

Cs+ , Sr2+

96

complexes are more soluble in ionic liquids and hence transfer

of an ionic species must be accompanied by either an ion of
opposite charge from the aqueous phase or an ion of the same
charge from the ionic liquid going into the aqueous phase.
The mechanism of metal transfer has been studied by a
number of groups and it has been found to differ from most nonaqueous solvents primarily due to the differences in speciation
of the metal as it transfers. An example of this can be seen with
the extraction of strontium from aqueous nitric acid solutions
using an 18-crown-6 ligand. When non-aqueous solvents are
used two axial nitrate ligands bind to the metal centre resulting
in a neutral strontium complex. When C5 mim Tf2 N was used
as an extraction phase, axial water ligands result in a cationic
strontium complex transferring.77,78 Acidic and neutral ligands
while less widely studied show interesting parallels to molecular
non-aqueous solvents with predominantly neutral complexes
being transferred. This enables easier prediction of extraction
behaviour.
Dietz et al. studied the partitioning of sodium ions between
HNO3 and C5 mim Tf2 N using an 18-crown-6 complexing
agent. It was shown that an extremely complex mechanism
was involved in the extraction which may involve up to
three pathways including neutral, anionic and cationic species
transfer. The extent of these different mechanisms was controlled
by the pH of the aqueous phase and the hydrophobicity of the
cation.79
Kozonoi and Ikeda used butyl-3-methylimidazolium nonauorobutanesulfonate to extract a range of metals from aqueous
solutions including Li+ , Na+ , Cs+ , Ca2+ , Sr2+ and La3+ . They
found that the extreme hydrophobicity of the highly uorinated
476 | Green Chem., 2011, 13, 471481

Ref.

anion meant that metal ion transfer could be mainly ascribed to

the cation exchanges between two phases.80
In an interesting recent development Liu et al. have used ionic
liquids supported on silica particles to extract rare earth metal
ions. High extraction coefcients were obtained using binary
mixtures of imidazolium and phosphonium ionic liquids.81
These materials begin to take on some of the properties of an ion
exchange resin i.e. high interfacial surface area. These materials
are easier to modify as there is simply a physical interaction
between the ionic liquid and the support.
A more thorough review of neutral ligands is given by Dietz82
which was updated for the separation of actinides and ssion
products.83 Other reviews on the subject include those by Reddy
et al.84,85 Slight caution should be used when regarding ionic
liquids as a simple drop-in replacement for organic solvents.
Dietz et al. showed that even though some ionic liquids are
immiscible with water the inclusion of neutral extractants can
increase the mutual solubility of both liquids which decreases
the efciency of the extraction process.86

Task specic ionic liquids (TSIL)

This term was coined by Davis87 to describe a liquid which had
been synthesised with functional moieties to perform a specic
task. Designing task specic ionic liquids is a novel and useful
concept of making the ions of the ionic liquid full two roles; as
both a solvent and complexing agent by chemically modifying
one of the constituents. Some examples of task specic ionic
liquids are shown in Table 3. Early examples attached functional
groups to the cation. This generic methodology is extremely
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versatile and just involves adding a complexing moiety onto a

quaternary ammonium functionality. In an alternative approach
a complexing agent is used as the anionic component. The
term TSIL is not useful now as most liquids are designed for
a given application and a more suitable description would be
functionalised ionic liquids.
Visser et al.36,88 developed a new class of task-specic ionic liquids with monoaza-crown ether fragments covalently attached
to the imidazolium cations and showed that they can be used
for the biphasic extraction of Cs+ and Sr2+ . Urea- and thioureafunctionalities were added to imidazole cations with PF6 - anions.
Extraction efciencies of these liquids for Hg2+ and Cd2+ are
reported to be several orders of magnitude larger than organic
solvents. Studies were also carried out using mixtures of the
TSIL with 1-alkyl-3-methylimidazolium][PF6 ] and it was shown
that the extraction efciency was dependent upon the proportion
of TSIL.
Nockemann et al.89 have used protonated betaine bistriamide
salts to dissolve metal oxides such as UO2 , ZnO, CdO and
HgO. The metal salts can be stripped from the ionic liquids by
treatment with acidic aqueous solutions. The two phases were
miscible above 55 C but separated below this temperature. This
was followed by a more in-depth study of cations functionalised
with carboxylate groups. These were shown to be effective at
dissolving a wide range of metal oxides although the solubilities
were not quantied.90
Papaiconomou et al.95 studied the distribution coefcients
of 14 metal ions into a range of pyridinium, pyrrolidinium
and piperidinium liquids with BF4 - , triuoromethyl sulfonate
and nonauorobutyl sulfonate anions. They showed good
extraction for mercury ions although the other metals were
not signicantly extracted. Good extractive selectivity could,
however, be obtained by putting functional groups such as
disulde or nitrile on the cations. Aminodiacetic acid moieties
were added to imidazolium cations as di-t-butyl esters.91 These
were shown to be effective chelators for Cu2+ , Ni2+ and Co2+
from aqueous solutions. It is clear therefore that a range of
generic synthetic methods have already been devised to produce
modied cation structures. There is a signicant scope to tailor
new metal specic cations, and the high cost of synthesis can be
offset by supporting the ionic liquid on inorganic or polymeric
substrates.
An alternative approach is to use a well-known anionic
complexing agent as the anion of the ionic liquid. This
approach was used by Jensen et al.92 who studied the extraction of lanthanides using 2-thenoyltriuoroacetone (Htta)
in a biphasic room-temperature ionic liquid-water system. It
was reported that anionic complexes of the form Nd(tta)4 - or
Eu(tta)4 - were produced when 1-butyl-3-methylimidazolium bis(triuoromethyl)sulfonylimide was used as the solvent. This contrasts with the hydrated and neutral complexes, M(tta)3 (H2 O)n
(n = 2 or 3), that form in non-polar molecular solvents. The
formation of anionic lanthanide complexes requires the transfer
of anions from the ionic liquid into the aqueous phase.
A similar approach was used by Mehdi et al.97 who used alkyl
imidazolium-based ionic liquids containing hexauoroacetylacetonate anions for the extraction of Nd3+ , Co2+ and Cu2+ .
The speciation of the metals was conrmed using X-ray crystallography and [C4 mim][Nd(hfac)4 ] and [C4 mim][Co(hfac)3 ] were
This journal is The Royal Society of Chemistry 2011

isolated. Work by Egorov et al. used trioctylmethylammonium

salicylate to extract Fe3+ , Cu2+ , Ni2+ and Mn2+ from aqueous
solutions.98 Interestingly this study also used the salicylatebased ionic liquid to modify an electrode surface and showed
that stripping voltammetry could be used to determine the
concentration of metal ions in the aqueous solutions. Although
not suggested by the authors, this technology could potentially
be used for direct, selective electrowinning of metals from
aqueous solutions. The use of task specic ionic liquids has
been reviewed separately by Davis.87

Electrowinning and cementation

Few studies have been carried out on electrowinning from
complex mixtures for the purpose of metal recovery per se. The
electrochemistry of numerous metal salts has been studied in
a wide variety of ionic liquids. A comprehensive review has
been published in a recent book.30 The lack of consistency and
understanding of reference potentials, speciation, electrode materials and temperatures makes comparison and interpretation
difcult.99
Since electrowinning is one of the most common methods of
extracting metals from solution, the electrochemical window,
which is the potential range of which the electrolyte is neither
oxidised nor reduced at the electrode surface, is very important.
Some ionic liquids have a very large potential window of up
to 4.15 V for [C4 mim][PF6 ] at a Pt electrode100 and 5.5 V for
[BMP][Tf2 N] at a glassy carbon electrode.101 The importance
of potential windows is well known from aqueous processes
where hydrogen evolution can be hazardous and lead to brittle
electrodeposits (hydrogen embrittlement). Ionic liquids may
even be chemically altered and hence destroyed if potential
limits are not considered. The wide potential window of ionic
liquids makes it possible to electrodeposit elements with low
redox potentials that cannot be reduced in other media such as
Al,102 Mg,103 Ge104 and Si.105
In principle metals can be selectively electrowon from complex
solution mixtures when there is a sufciently large difference
in the reduction potential. Our recent work has surprisingly
shown that metal salts behave like ideal solutions in some ionic
liquids.106 This is an important result as redox potentials can
be predicted as a function of concentration without having to
take account of the activity coefcient. Nernstian behaviour for
metal salts has been obtained for solutions up to 1 mol kg-1 .
This work has also included for the rst time the cell potential
for a hydrogen electrode, which is also shown to be Nernstian
and from this the rst standard redox potentials were calculated
for the Ag+/0 and Cu2+/+ systems and standard thermodynamic
properties were determined.
In aqueous solutions, redox potentials can be selectively
shifted by judicious choice of an appropriate ligand. While in
principle the same could be achieved using the same ligands in
ionic liquids the relative strengths of possible metal-anion complexes is largely unknown and remains an important parameter
to quantify. We have recently developed the rst comparable
electrochemical series in two deep eutectic solvents55 and similar
studies are urgently needed in ionic liquids with discrete anions
for comparison. We are currently studying the relation between
speciation and redox potential for a range of anion basicities.
Green Chem., 2011, 13, 471481 | 477

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There are a number of technical issues to be addressed in the

electrowinning area. One issue is the counter-electrode reaction;
in water it is generally oxygen evolution at the anode, but
clearly decomposition of the ionic liquid is undesirable in an
ionic liquid. The alternatives would be a soluble metal anode,
which is also undesirable or a sacricial species which produces
a gas upon oxidation. An alternative scenario is to use an
electrocatalyst to oxidise metallic substrates and collect the metal
at the cathode.

oxides but it led to a greatly reduced viscosity (56 cP at 298 K). It

was noted that upon scale up to pilot plant extraction efciency
improved due to better stirring in the tank. Also, the addition
of particles into the ionic liquid lowered viscosity further as the
particles break up the structure of the ionic liquid and aid mass
transport.24 Fig. 5 shows a ow diagram and a photograph of
the plant used to carry out a large scale test on the efcacy of
using ionic liquids for metal extraction.

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Electroreduction
Giridhar et al. showed the rst example of a direct extraction of
a metal from an aqueous solution into an ionic liquid followed
by direct electrolysis of the metal from the ionic liquid.107 Tri-noctylmethylammonium chloride and nitrate were used to extract
palladium from a nitric acid solution. It was shown that Pd
could be directly deposited onto an electrode in the ionic liquid
phase. It was, however shown that appreciable amounts of water
and acid were carried over to the ionic liquid and high acid
concentration decreased the metal extraction efciency.
In a model experiment with copper/zinc mixtures we have
shown that the metals can be electrowon into their composite
materials by using the difference in redox potentials of these
metals. Copper needs to be electroreduced rst due to having
the higher redox potential. The cathode is changed, the voltage
is increased and zinc is nally deposited. This was used as a
follow-on process of the iodine based electrocatalytic oxidation
mentioned above.55
Cementation
A commonly used alternative to electrowinning is cementation.
In this process a more reactive metal (generally in the form of
a nely divided powder) is mixed with the extract. The metal
from solution chemically oxidises the additive and becomes
deposited on its surface. While commonly used in aqueous
solutions it cannot be used in acidic matrix due to the hydrogen
evolution side reaction. So far, it has only been applied for the
extraction of lead from electric arc furnace dust using ionic
liquids (see below). The advantage of this technology over the
corresponding aqueous solution is that the deposit obtained is
porous ensuring complete dissolution of the sacricial additive
and the efcient extraction of metal from solution. Despite
the lack of fundamental data for cementation we were able to
characterise the immersion coating of silver on copper,108,109 and
this has been set up on a commercial scale for printed circuit
board coating.110

Large-scale study
These techniques have been applied to the recovery of Zn and
Pb from a waste material produced by the electric arc furnace
(EAF).42 A Deep Eutectic of choline chloride and 2 urea showed
selectivity in EAF dust towards just zinc and lead oxides, while
iron and aluminium oxides were insoluble. Due to relatively high
viscosity of the liquid (~800 cP at 298 K) a hybrid liquid using
a second hydrogen bond donor was used. A ratio of 1 choline
chloride : 1.5 ethylene glycol : 0.5 urea showed no major change
to the solubility of zinc or lead oxides and insolubility of iron
478 | Green Chem., 2011, 13, 471481

Fig. 5 Photograph and schematic diagram of the pilot plant built to

extract lead and zinc from electric arc furnace dust.

Both Zn and Pb could be electrowon, but due to their order

in the electrochemical series, lead would have to be electrowon
rst. As lead is not a high-priced element, it is not economically
worth extracting, so it is better to be cemented. By the addition
of a metal with lower redox potential (in this case Zn dust),
lead was precipitated. Cementation is inefcient in aqueous
systems because the immersion deposit is dense and precludes
dissolution of underlying metal but in deep eutectics the deposit
is porous and allows lead levels in solution to be decreased down
to 12 ppm.
Subsequently zinc could be electroplated with a maximum
current efciency of 75%. For more expensive metals this would
be ne, but it is not economically efcient enough for zinc
extraction. Zinc chloride was therefore precipitated out using
ammonia to decrease the solubility. The solid was ltered and
the ammonia solution was boiled off, leaving just the ionic liquid
to be used again. This made the process economically viable since
zinc chloride had a higher value than metallic zinc.

Technical issues
With certain aspects of the technology entering scale-up trials
there are numerous technical aspects that need to be addressed
before ionic liquids can be practically applied to metal processing. Most of the issues will resolve around the two fundamental
differences with molecular solvents; namely cost and viscosity.
The rst and most important issue is ionic liquid recovery
and recycling as they will have to be used many times without
signicant loss to make the process economically viable. When
the metals are in aqueous solutions, the solubility of the ionic
liquid in water is an important issue. A more difcult issue to
address arises when the metals are extracted from a solid matrix.
Filtering solid dispersions in a viscous liquid clearly has complex
technical issues and settling rates will be an order of magnitude
slower than those in aqueous solutions. Combined with this
is the dichotomy of surface wetting; to obtain low solution
viscosity a low surface tension is essential but this causes issues
associated with the wetting of hydrophilic substrates. Removing
the ionic liquid from the solid matrix is also non-trivial since the
liquid does not evaporate. About the only option is to wash the
This journal is The Royal Society of Chemistry 2011

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solid with a molecular solvent and then evaporate the solvent

from the ionic liquid. The heat capacities of ionic liquids are
lower than those for aqueous solutions making solutions easier
to heat. Material compatibility is not such an issue since most
commonly used ionic liquids are inert to most polymers, metals
and ceramics.

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Intellectual property
In terms of the IP literature, there are comparatively few patents
compared to most application elds. These can be divided
into new types of ionic liquids and new extracting methods.
Rogers and Holbrey111 patented the use of perhalide anions
for metal recovery. The redox potentials of halides are above
those of most metals and they therefore make excellent oxidising
agents because the reduction of the perhalides is very reversible.
Framroze112 used HF dissolved in ionic liquids to improve the
extraction efciency of metals from recalcitrant refractory ores.
The proposed process involves treating the ore with HF in an
ionic liquid followed by aqueous NaCN solutions.
Ekman et al.113 proposed a method to recover metals from
a contaminated supported catalyst using ionic liquids. An antisolvent was added to the solution to separate the metals from
any organic contaminant. It was proposed that the metals could
be separated from the solution by precipitation, ion exchange,
solvent extraction, electrodeposition or chromatography. Chen
et al.114 used an acrylate resin XAD-7 impregnated with ionic
liquid by immersing in Cyanex 923 containing an ionic liquid.
It was claimed that the ion exchange resin thus formed could
be used to extract metal ions such as Sc3+ , Yb3+ , Er3+ , Ho3+ and
Y3+ . The betaine- and choline-based systems discussed above
have been patented by Binnemans et al.115 and Abbott et al.116

The next step

Hydrometallurgy is clearly going to continue to be the dominant
technology for metal extraction and processing due to cost and
volume constraints. Its application to new matrices is facilitated
by the wealth of information in existence about speciation as
a function of pH and redox potential. Ligands for extraction
are well known, versatile and selective. The incompatibility
of some metals with aqueous processing due to their toxicity
e.g. lanthanides and actinides mean that there is potential
for alternative solvent technology for metal processing. The
potential to more selectively separate metals using ionic liquids
means that there may also be signicant application for these
neoteric solvents in metal recycling. It could be questioned
whether ionic liquids provide any environmental advantages. To
date few have been conclusively proven but clearly the most
potential could be achieved through process intensication.
Solubilities of metal salts in ionic liquids have been shown
to be comparable with acidic aqueous solutions but only for
a few systems. As extraction media, however, ionic liquids
demonstrate much higher solubilities for metal salts than most
organic solvents. In identifying the way forward for ionic liquids
in the application eld, it is necessary to highlight the unique
advantages that ionic liquids provide. These are the potential
ability to simplify processing techniques and circumvent oxide
and hydroxide products during processing. The areas where this
This journal is The Royal Society of Chemistry 2011

may have unique application is in the processing of platinum

group metals where similar reactivities and speciation makes
separation protracted and complex and the other is in lanthanide
and actinide separation.
This review reveals that most aspects of metal processing have
been addressed using ionic liquids, although not many of them
in signicant detail. To extend the eld, a signicant amount
of fundamental work needs to be carried out into speciation of
metals in ionic liquids as a function of anion Lewis basicity. This
information needs to be fed into solvation studies to understand
the effect of speciation on redox potentials and solubility. Ionic
liquids present a viable alternative for the processing of metals,
although it is likely that these will focus on niche applications.
Any green advantages will come from process intensication
and the avoidance of producing large volumes of dilute aqueous
waste containing heavy metals.

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