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Direct extraction of copper from copper sulfide

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Cite this: Green Chem., 2019, 21,

minerals using deep eutectic solvents†
6502
Syahrie Anggara,a Francesca Bevan,a Robert C. Harris, a Jennifer M. Hartley, a,b

Gero Frisch, b Gawen R. T. Jenkin c and Andrew P. Abbott *a

Received 12th September 2019,
Accepted 8th November 2019
DOI: 10.1039/c9gc03213d
rsc.li/greenchem
Copper is predominantly recovered from sulfide ores by pyrometallurgy – an energy intensive process
requiring capture and treatment of released SO2. Whilst some copper ores are amenable to hydrometal-
lurgy, chalcopyrite, the main copper mineral, is challenging to process in aqueous solutions due to
surface passivation. The chalcopyrite surface may be less prone to passivation in non-aqueous solvents
such as Ionic Liquids. Here we provide the first demonstration that electrochemistry in Deep Eutectic
Solvents can solubilise and directly recover high purity copper from solution from three copper sulfide
minerals: covellite (CuS), chalcocite (Cu2S) and chalcopyrite (CuFeS2). Cyclic voltammetry supported by
EXAFS identifies the metal speciation in solution. In a choline chloride-ethylene glycol DES the main
copper species present after dissolution of chalcocite and covellite was [CuCl4]2−. In the solution formed
from chalcopyrite, a mix of CuII and CuI species were formed instead. In a choline chloride-urea DES,
copper had a mixed chloride/O- or N-donor coordination, potentially altering electrochemical behaviour.
Sulfide in the mineral is oxidised to sulfate without the generation of SO2 or H2S. The best selective recov-
ery of copper (99 at%) from chalcopyrite was obtained with a mixed DES of 20 wt% choline chloride-
oxalic acid and 80 wt% choline chloride-ethylene glycol. This demonstrates how design of the Deep
Eutectic Solvents can enable increased selectivity of copper over iron in the electrowinning stage by
changing solute speciation and redox properties.

Introduction contain high concentrations of acid or base, and can involve

Copper ores are most commonly processed through pyrometal-
lurgical methods, and currently around 84% of copper (nearly
17 million tonnes per annum) is produced this way, domi-
nantly from chalcopyrite ores that are not amenable to
hydrometallurgy.1–3 Ores with significant impurities, such as
>1% arsenic, present environmental and technical challenges
for smelters and alternative process methods are desirable, i.e.
hydrometallurgical methods which use aqueous solutions to
solubilise metal species,4,5 after which the metals are sub-
sequently recovered by methods such as precipitation, electro-
winning, cementation, or ion exchange.2 However, these tra-
ditional methods for the processing of metals often have high
energy usages and/or utilise corrosive solutions, which can
a
Department of Chemistry, University of Leicester, Leicester, LE1 7RH, UK.
E-mail: apa1@le.ac.uk
b
Institut für Anorganische Chemie, TU Bergakademie Freiberg, 09599 Freiberg,
Germany
c
School of Geography, Geology and the Environment, University of Leicester,
Leicester, LE1 7RH, UK
† Electronic supplementary information (ESI) available. See DOI: 10.1039/
c9gc03213d
the production of acidic gases such as H2S and SO2, especially
where sulfide minerals are the main feedstock.6
The secondary-enriched oxide and sulfide zones of copper
deposits that are formed near-surface in the weathering zone
are characterised by copper oxides, carbonates, and sulfide
minerals such as chalcocite (Cu2S) and covellite (CuS) that are
easily and economically processed by heap leaching with sulfu-
ric acid. However, as these easily exploitable near-surface
deposits become exhausted, the deeper lower grade primary
ores dominated by chalcopyrite (CuFeS2) are increasingly
being exploited. Chalcopyrite, which accounts for approxi-
mately 70% of world copper reserves,7 is extremely difficult to
leach under hydrometallurgical conditions. It has been
suggested that slow dissolution rates are due to passivation of
the mineral surface via growth of an impermeable sulfur or
polysulfide layer.8,9 Aqueous leachates for chalcopyrite can
require high temperatures,10 additives such as ferrous/ferric
species11,12 and peroxides,13 although more environmentally
friendly methods such as microbial leaching have also been
investigated.1,14
In an alternative drive to improve the environmental
hazards of classical acidic and caustic hydrometallurgical pro-
cessing, ionometallurgy has been proposed as an alternative

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approach. Ionic liquids (ILs) enable high solubility of metals
salts and wide electrochemical windows, which are useful pro-
perties for mineral processing.15 Interestingly, it has been
observed that the presence of chloride ions in aqueous solu-
tions can increase the rate of chalcopyrite leaching due to the
formation of chlorocuprate(I) ions,16 and a key property of ILs
is their high anionic component content. As the anionic com-
ponent of the IL generally controls speciation of metals, the
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need for highly coordinating additives is reduced, potentially
allowing novel dissolution routes. Investigations into the leach-
ing of chalcopyrite in imidazolium ionic liquids indicate a
highly complex dissolution mechanism, with sulfide and poly-
sulfide species forming in many liquids.17 The presence of
FeIII species in IL media has an analogous effect to aqueous
media, with the initial rate of chalcopyrite leaching being
improved compared to a FeIII-free system.18 [C4mim][HSO4]
has been suggested as an alternative to H2SO4 as a leachate for
chalcopyrite, due to its ability to catalyse the transfer of oxygen
and accelerate the oxidation of chalcopyrite,19,20 with the
potential for solvent recyclability.21
It has been reported by Carlesi et al.22 that acidic ILs con-
taining the [HSO4]− anion can promote chalcopyrite dis-
solution in combination with 1 M H2SO4. It was observed that
[C6mim][HSO4] and [C4mim][HSO4] both exhibit some capacity
to dissolve chalcopyrite at higher temperatures, however there
were no clear advantages over simple leaching with H2SO4. It
was observed, however, that when these ILs were used in com-
bination with 1 M H2SO4 in equal volumetric amounts, copper
recovery rates were greatly improved (∼70%) in comparison to
the aqueous leaching (∼24%) when the temperatures exceeded
60 °C. It was proposed that the main role of the IL is to enable
continuous acid leaching by promoting the decomposition of
potential sulfidic intermediates that can passivate the surface
of the chalcopyrite. Carlesi also suggests that the hydrophobi-
city of the IL is important in removing oxidation products that
are insoluble in aqueous media from the surface of the chalco-
pyrite. This has been supported by Albrecht et al.23 who tested
a range of HSO4− ILs and found that the hydrophobicity of the
IL plays a key role in its effectiveness as a potential lixiviant for
chalcopyrite. It was observed in this study that ILs
[C1mim][HSO4] and [NH4][HSO4] were the best performing and
demonstrated that the higher the polarity the cation is, the
poorer the wetting of the surface of the chalcopyrite. This in
turn resulted in higher Cu extraction rates than the less polar
ILs investigated. Hu et al.24 demonstrated that ILs combined
with hydrogen peroxide (H2O2) as an oxidant can yield high
yields (>98%) of Cu from chalcopyrite in 2 h at 45 °C. The use
of ILs in commercial applications is however severely limited
by their relatively high cost and so full scale applications using
this technology become very difficult to justify.
Chloride leaching of chalcopyrite has been shown to be a
potential alternative to the majority of sulfate-based lixiviants,
which often exhibit low kinetic rates of dissolution of
chalcopyrite.25,26 Early work had demonstrated that chloride-
based lixiviants such as aqueous CuCl2 and FeCl3 could
recover >95% of Cu from chalcopyrite. A mixed chloride-
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sulfate bath was demonstrated in work carried out by Jeffrey
et al.,27 who showed that adding 0.5 M NaCl to a 1 M H2SO4
solution significantly reduced the rate of passivation of chalco-
pyrite during electrochemical oxidation. Fuentes-Aceituno
et al.28 demonstrated that electro-assisted dissolution of chal-
copyrite in a 2 M HCl solution exhibits a greater efficiency of
chalcopyrite dissolution than in analogous H2SO4 solutions.
In both cases this improved dissolution rate of chalcopyrite in
the chloride-containing systems is due to the destabilising
effect chloride has on the sulfide-based passivation layer that
forms during the dissolution of chalcopyrite. Dreisinger
et al.29 devised a number of process flowsheets using solutions
of either CuCl2·2H2O or FeCl3 that resulted in Fe-free Cu solu-
tions, which could then be transferred into a conventional
sulfate-based electrowinning circuit. In both processes >95%
of the Cu in chalcopyrite could be extracted, with dissolved Fe
precipitated out as hematite (Fe2O3) or goethite (FeOOH).
Deep Eutectic Solvents (DESs) are primarily chloride based
media that offer similar properties to ILs, however they are
cheaper and easier to produce on a large scale and can be
designed to have low toxicity.30 DESs have been demonstrated
to be effective in the dissolution and extraction of other
metals, for example in the oxidation of gold31,32 and several
sulfides,33,34 rare earth carbonates,35 or in the processing of
electric arc furnace36 and flue dusts.37 The current study inves-
tigates the electrochemical behaviour of three common copper
sulfide minerals in DES media. Chalcopyrite is composed of
monovalent copper with trivalent iron in a monosulfide:
CuIFeIIIS2.38 Covellite and chalcocite are both also thought to
contain monovalent copper, but chalcocite is a simple mono-
sulfide, whereas covellite is a mixed monosulfide and disul-
phide mineral.39,40 Their electrochemistry is explored using a
paint casting method, and the speciation of the dissolved
metal ions is characterised via spectroscopic methods. A novel
bulk digestion and recovery process for high purity copper
from natural chalcopyrite is demonstrated, whilst avoiding
hazardous by-products such as H2S or SO2. Through the use of
hybrid DESs, we highlight the potential of ionometallurgy for
the processing of copper ores by judicious tuning of the DES
composition to obtain a high purity of electrowon copper.
Experimental
All DESs were made using the methods described in previous
publications.41,42 Mixtures were made with 1 mol. eq. of
choline chloride (ChCl) and 2 mol eq. of ethylene glycol (EG),
urea (U), or 1 mol equivalent of oxalic acid dihydrate (Ox),
hereafter referred to as 1ChCl:2EG, 1ChCl:2U, and 1ChCl:Ox,
respectively. All chemicals were obtained from Aldrich, with
purities of >99%.
Natural covellite (sample 20582 from Butte Montana) and
chalcocite (non-curated sample) were obtained from the
School of Geography, Geology and the Environment at the
University of Leicester, whilst natural chalcopyrite was sourced
from Morocco. Powder X-ray diffraction (XRD) was carried out
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with a Phillips model PW 1730 X-ray generator on both the
synthetic and natural samples in order to confirm that their
crystal structures are the same. Both natural and synthetic CuS
had similar XRD patterns consistent with the ICSD database
entry for covellite, confirming that the synthetic CuS has a cov-
ellite structure. The XRD pattern for synthetic and natural
chalcocite showed diffraction peaks consistent with chalcocite
in the ICSD database, but the natural sample showed some
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additional peaks, suggesting that there may be slight impuri-
ties. Zeiss EDX analysis was carried out on the natural chalco-
pyrite to determine mineral and impurity content of the
ground and sieved material. This material had an average com-
position of 80.5% chalcopyrite, with 10.7% quartz and 3.9%
pyrite as the major impurities. In decreasing order, the
remaining 4.9% of the material consisted of galena, magnetite,
barite, covellite, sphalerite, clinopyroxene and chalcocite. The
average elemental composition of the chalcopyrite was close to
stoichiometric, and had minimal inclusions of other minerals.
The natural mineral samples were ground with a fly press
and TEMA mill, and homogenised via riffling. The material
was then passed through a 300 µm sieve, and the fraction that
did not pass through a further 100 µm sieve was used in the
paint casting experiments.
Electrochemical measurements
Cyclic voltammetry (CV) experiments were carried out using the
paint casting method, previously described by Abbott et al.,33
unless otherwise stated. The pastes which were painted onto the
electrodes were formed by finely grinding ca. 2 mg of copper
mineral powder with 100 mg of DES, before being spread evenly
on the surface of a Pt flag working electrode and immersing in
the electrolyte (same DES as used to make the paste).
Fig. 1 The cell design used in the experiment. Left: Before the experiment and right: after the experiment was completed, showing the different
layers of material present. Colours differed depending on DES used.
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An Autolab Type III potentiostat with GPES software was
used for electrochemical measurements. All CVs were first
swept to positive potentials, starting from an initial potential
where no redox events were taking place. A three electrode
system (2× Pt flag and a 100 mM Ag/AgCl reference) was used
for CV experiments. The electrode potentials discussed here
were estimated from averages of peak onset values. All CVs
were carried out at 5 mV s−1.
For bulk dissolution and electrolysis experiments, a 2 elec-
trode system was used. For dissolution experiments, iridium
oxide-coated titanium mesh was used as both an anode and
cathode, and the mineral paste was ‘painted’ onto the surface
of the mesh before being electrolysed for 24 h at a constant 1.5
V. In the case of the bulk electrolysis, a Ni plate was used as
the cathode and an iridium oxide-coated titanium mesh anode
was submerged into a porous tube containing a paste of ca.
50 g of the mineral. A schematic of the bulk electrolysis cell is
depicted in Fig. 1. Bulk electrolysis was carried out at a con-
stant current density of 0.2 mA cm−2 and for each sample, the
Ni cathode was replaced every 24 h. The resulting plated
deposits were analysed with a Hitachi S-3600N Environmental
Scanning Electron Microscope (SEM) with Oxford INCA 350
energy-dispersive X-ray spectroscopy (EDX) software in order to
determine their morphology and composition. The precipi-
tates remaining at the bottom of the cell after electrodissolu-
tion were collected, dried and weighed and their composition
was analysed with EDX.
Spectroscopic measurements
All UV-Vis spectra were recorded using an UV5Bio (Mettler
Toledo) UV-Vis spectrometer between 190 and 1000 nm. The
Fe- and Cu-speciation of anodically dissolved copper min-
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erals were determined by extended X-ray absorption fine
structure (EXAFS), at BM26A of the ESRF synchrotron.43
Measurements were carried out at the Fe and Cu K-edges,
nominally 7112 and 8979 eV, respectively. Transmission
data were measured using ionisation chambers, whilst fluo-
rescence data were measured with a nine-element Ge solid-
state detector operating on seven elements in total fluo-
rescence yield mode. The monochromator was a Si(111)
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double crystal. Copper and iron foils were used as a refer-
ence sample for amplitude calibration. Liquid samples were
kept in a flat Perspex sample holder, with a sample chamber
of 15 × 8 mm, at 1.5 mm thick, with 40 µm Kapton foil
windows. The samples were aligned at approximately 55°
with respect to the X-ray beam, with the fluorescence detec-
tor placed perpendicular to the X-ray beam in order to mini-
mise any elastic scattering signals. Two to four spectra were
recorded for every sample, then averaged, calibrated and
background subtracted with the program Athena.44 The
EXAFS spectra were fitted using EXCURV45 to calculate
interatomic distances and their root-mean-square variations
(σ2). Electron scattering parameters were calculated and
used to determine the type and number of coordinating
atoms, using the Hedin–Lundqvist potential.46 Quoted
uncertainties on fitted parameters are equal to two standard
deviations.
ICP analysis
The copper and iron concentrations of the samples were deter-
mined via ICP analysis using a Thermo Scientific iCAP Qc
ICP-MS. Samples were calibrated against standard solutions
containing known amounts of copper and iron chlorides.
Samples were prepared via 1 : 10 or 1 : 100 dilution in deio-
nised water, after which 2 drops of HNO3 were added to
prevent any precipitation. Where the copper concentration was
too low to obtain a good signal-to-noise ratio in the EXAFS
(<2–5 mM), UV-vis spectra were recorded and compared to
spectra of known species to obtain a good indication of the
species present.
Fig. 2 CVs of (a) synthetic chalcocite (Cu2S) with overlaid CuCl2 (blue), and (b) synthetic covellite (CuS) with overlaid Na2S (red) obtained via paint
casting onto a Pt flag electrode in 1ChCl:2EG, with Ag/AgCl reference electrode.
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Results and discussion
Paint casting of Cu-based sulfide minerals
Paint casting of minerals using DESs was first introduced by
Abbott et al.33 as a method to study the electrochemistry
of galena (PbS) without the inclusion of additional
binding agents. It was demonstrated that, even though the
mineral itself is relatively insoluble in the DES, the
electrochemical properties of both Pb and S could be studied,
since well-defined oxidation and reduction peaks for both
species could be observed. Application of this method to Fe
and As sulfide minerals, such as pyrite and arsenopyrite,
showed that the method was applicable to a range of
minerals.34
In the present study, the paint casting method was applied
to three Cu-based sulfides and copper chloride compounds.
Fig. 2 shows the cyclic voltammograms (CVs) obtained from
synthetic copper sulfides, copper chloride and sodium sulfide.
Paint casting CuCl2 produces a CV that is identical to that of a
solution of CuCl2 in 1ChCl:2EG measured at a conventional Pt
disc electrode,47 with average onset potentials of 0.436 V and
−0.335 V vs. AgCl reference for the CuII/I and CuI/0 couples,
respectively, highlighting that this method produces results
that can be directly be compared to traditional solution based
CV measurements. Sodium sulfide displays a redox process at
ca. 0.25 V that could potentially be oxidation of S2− to elemen-
tal sulfur or sulfate.
Interestingly, the chalcocite and covellite paint castings
show three separate redox couples. These can be related to the
electrochemistry of both Cu and S, in a similar manner to that
obtained from paint casting PbS, where both Pb and S were
electrochemically active.33 The redox couple unrelated to the
copper processes is within the same potential range as sulfide
oxidation. Similar peaks were observed during measurements
involving pyrite,34 but not the other iron sulfide minerals such
as marcasite or pyrrhotite, or those containing arsenic. This is
important, as it may indicate if oxidation of the sulfide moiety
of the mineral is key to the dissolution mechanism.
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Fig. 3 Voltammograms of covellite at different loadings (left), and effect of covellite to alumina loading (right). All measurements carried out in
1ChCl:2EG.
The corresponding paint casting experiments were also
carried out in 1ChCl:2U and 1ChCl:Ox. However, in 1ChCl:2U
the high viscosity (750 cP)48 of the solution resulted in CVs
that were very broad and the individual redox couples could
not easily be resolved. During measurements of covellite in
the acidic DES 1ChCl:Ox, a strong H2S-like odour was detected,
and further experiments in the neat liquid were not attempted.
Effect of paste loading and presence of inactive material
In previous work, the mineral galena (PbS) was shown to
demonstrate a clear electrochemical response in the solid state
and a linear correlation was observed between the total anodic
charge and the mass of mineral on the anode surface.33 Here,
we investigate the effects of paste loading of the anode, using
synthetic covellite in 1ChCl:2EG.
Fig. 3a shows the electrochemical response when different
masses of covellite are loaded onto the electrode surface. The
CVs retain the same form and potentials as the mass of covel-
lite increases. The total current increases linearly with covellite
loading, indicating that current efficiency remains similar
when using covellite loadings of up to 2 mg on the electrode.
However, this data is not representative of a true ore sample
since it does not contain gangue material. Often these gangue
minerals are chemically and electrochemically inert, e.g. sili-
cates or carbonates, and are not homogeneously distributed
throughout ore bodies.
Fig. 4 Voltammograms of (a) natural covellite, (b) natural chalcocite, and (c) natural chalcopyrite in 1ChCl:2EG. All were pasted onto the anode
surface (Pt flag electrode).
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To demonstrate the effect of mineral dilution on the
electrochemical response a ‘synthetic’ gangue (alumina) was
added to covellite in different proportions, but each experi-
ment had a total covellite + alumina content of 2 mg. The
effect of loading is demonstrated in Fig. 3b, where it can be
seen that the overall shape of the CVs and values of electrode
potentials are not significantly shifted by the presence of this
gangue material. CVs of covellite and chalcocite (Fig. 4) were
almost identical to those of the synthetic material, indicating
that electrochemically inactive gangue materials do not
adversely affect the electrochemical behaviour of the copper
sulfide other than by dilution or increasing the resistivity of
the paste.
Electrochemical dissolution of chalcopyrite (CuFeS2)
In aqueous systems chalcopyrite is significantly more difficult
to dissolve chemically than covellite and chalcocite due to
surface effects, such as the generation of polysulfide
species,9,49 with leaching processes commonly requiring high
temperatures or high pressures.5,50 The presence of Cl− ions
has been suggested to alter the morphology of any surface
sulfur formed, allowing the chalcopyrite to leach more easily
by preventing passivation.51 Additionally, the influence of iron
species must be considered, as the formation of insoluble iron
oxide/hydroxide phases in aqueous sulfate systems has been
observed if the system was heated or electrolysed too fast.52
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DESs provide a high Cl− ion content and low water content,
whilst reducing the need for either high additional salt or acid
concentrations, circumventing most oxide chemistry.30
Therefore, they should provide a suitable environment for
chalcopyrite dissolution. Paint casting was carried out directly
on the natural material, and the CV of chalcopyrite resembles
that of covellite more than chalcocite, displaying the oxidation
and reduction peaks associated with CuII/I (0.422 V), along
with the reduction peak for CuI/0 (−0.354 V, onset only) but
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not the corresponding stripping peak (Fig. 4c). In aqueous
leaching systems, it has been suggested that chalcopyrite is
first converted to Cu2S, and additional peaks in the CV are
related to a mixture of other Cu-sulfide species, such as
Cu1.92S, Cu1.60S, and CuS.9 Alternatively, the presence of chlor-
ide in aqueous leachates is known to change surface sulfur
into a more crystalline and porous form,51 which may also
take place in DES media. The lack of defined peaks for the
FeIII/II couple is most likely due to an overlap with the CuII/I
redox couple as both redox couples have similar electrode
potentials (see Fig. S2, ESI†).
Metal speciation after electrochemical dissolution in DESs
To determine the speciation of metal ions after electro-
chemical dissolution of the Cu-sulfide minerals, cyclic voltam-
metry (CV), along with a combination of UV-Vis and extended
X-ray absorption fine structure (EXAFS) spectroscopies were
employed. All three minerals were anodically dissolved in
1ChCl:2EG for a total of 24 h at 1.5 V, then the samples were
filtered to remove any particulate matter. Bulk dissolution of
both covellite and chalcocite produce very strongly coloured
yellow solutions (Fig. 5, inset), characteristic of the [CuCl4]2−
complex.53
After bulk dissolution of chalcopyrite, a light green/yellow
solution was produced. From the UV-vis spectra, different
species are expected to be present. Due to the pale colour of
the solution and change in wavelength of the absorption
maxima, the presence of a CuI species such as [CuCl2]− was
considered.53 As ICP analysis showed a 1 : 1 ratio of Cu : Fe in
solution, solutions were made containing a 1 : 1 mixture of
Fig. 5 UV-Vis Spectroscopy of solutions generated from bulk anodic
dissolution of covellite (CuS black), chalcocite (Cu2S red), and chalco-
pyrite (CuFeS2 blue) in 1ChCl:2EG.
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CuCl with either FeCl3 or FeCl2. The spectrum of the
CuCl : FeCl2 mix matched the closest, indicating that iron was
most likely in the +2 oxidation state, suggesting that FeIII has
been reduced, either at the cathode, or through the oxidation
of sulfide.
As UV-vis could only provide indicative information about
speciation, EXAFS was used to determine the speciation of
copper ions produced via electrodissolution of three copper
sulfides. From X-ray absorption near edge spectroscopy
(XANES), it is possible to obtain an indication of which oxi-
dation states are present.
EXAFS study of solubilised copper sulfide based minerals
Previous investigations into the speciation of high purity metal
chloride salts in IL and DES media revealed that coordination
was, in general, controlled by the anionic component of the
liquid.53 However, it is possible that metal speciation after
electrolytic dissolution of natural minerals may be altered due
to the presence of decomposition products from the solvent or
the other components in the minerals, such as anionic sulfur
species. Multinuclear species may also be formed under these
conditions.
For the solutions formed following anodic dissolution of
covellite and chalcocite in 1ChCl:2EG, tetrachloride species
with Cu–Cl path lengths of 2.24–2.25 Å were present, similar to
solutions of CuCl2 in 1ChCl:2EG (Table 1).47,53 XANES data
(Fig. 6) confirms that CuII is present in both cases, i.e. the CuI
in the minerals has been oxidised. Due to the sulfide content
of the samples, it is likely that various sulfur-containing
ligands will be present in solution. EXAFS cannot easily dis-
tinguish between Cl- and S-coordination; however, formation
of the Cl-species is most likely due to the high ca. 4.2 M chlor-
ide content of the DES.
Contrary to the two copper sulfide systems, a CuI species
was indicated for the anodic dissolution of chalcopyrite.
Coordination number, Cu–Cl path lengths, and thermal dis-
order were all of a similar magnitude to the parameters
obtained from a CuCl solution in the same DES. Due to the Fe
K-edge being softer, a much higher iron concentration is
required to obtain data with a good signal-to-noise ratio, there-
fore we cannot confirm the speciation or oxidation state of
iron in solution using EXAFS. However, it is known that iron
chloride salts form either [FeCl4]2− or [FeCl4]−, depending on
the iron oxidation state (Table 2). As the method of dissolution
has no apparent effect on the coordination of copper ions in
1ChCl:2EG, we propose that any soluble iron species formed
during electrodissolution are also likely to be chloride co-
ordinated. However, the possibility of Fe–S or Fe–O complexes
cannot be ruled out. As no Cu–Fe paths were observed in any
of the Cu-edge data, it is unlikely that mixed-metal species are
present in solution.
Near-edge measurements indicated that the oxidation state
of the electrodissolved copper changed based on the other
species present in the mineral. We propose that this change in
copper oxidation state of the solution species can be explained
via electrode potentials. In 1ChCl:2EG, the formal electrode
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Table 1 EXAFS fit parameters for solutions of copper salts and mineral dissolution in 1ChCl:2EG (top) and 1ChCl:2U (bottom)

Solute Coordinating atom/group Number of atoms, N Distance from Cu, r/Å Debye–Waller factor, a (Å2) Fit index, R1/%

CuCl2a Cl 3.7(2) 2.252(5) 0.008(1) 4.48%

a
CuCl Cl 2.4(2) 2.190(9) 0.016(3) 8.08%
CuS (covellite) Cl 4.4(2) 2.248(4) 0.012(1) 2.74%
Cu2S (chalcocite) Cl 4.3(4) 2.239(7) 0.010(2) 5.87%
CuFeS2 (chalcopyrite)b Cl 3.0(4) 2.21(1) 0.019(5) 15.21%

Solute Coordinating atom/group Number of atoms, N Distance from Cu, r/Å Debye–Waller factor, a (Å2) Fit index, R1/%
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CuCl2a Cl 3.9(3) 2.239(7) 0.013(2) 6.39%

a
CuCl Cl 2.5(2) 2.224(7) 0.012(2) 7.55%
CuS (covellite) O 1.4(3) 1.95(2) 0.007(3) 1.42%
Cl 1.9(4) 2.24(1) 0.015(3)
a
Data already presented in reference.53 b Data from single scan.

Fig. 6 XANES region (left) and k2-weighted Fourier transform (right) for CuCl2, covellite (CuS), and chalcocite (Cu2S) (top), and for CuCl and chalco-
pyrite (CuFeS2) (bottom) in 1ChCl:2EG. Data are circles and fits are lines. Spectra are offset for clarity.

Table 2 EXAFS fit parameters for solutions of iron salts in 1ChCl:2EG (top) and 1ChCl:2U (bottom)

Solute Coordinating atom/group Number of atoms, N Distance from Fe, r/Å Debye–Waller factor, a (Å2) Fit index, R1/%
a
FeCl2 Cl 3.8(2) 2.313(3) 0.0065(8) 2.88%
FeCl3 Cl 3.8(1) 2.205(3) 0.0042(7) 1.58%

Solute Coordinating atom/group Number of atoms, N Distance from Fe, r/Å Debye–Waller factor, a (Å2) Fit index, R1/%
a
FeCl2 O 4.8(4) 2.08(1) 0.019(3) 6.84%
FeCl3 O 4.8(3) 2.066(9) 0.017(3) 6.06%
a
Data already presented in reference.53

6508 | Green Chem., 2019, 21, 6502–6512 This journal is © The Royal Society of Chemistry 2019

Green Chemistry
potentials for the CuII/I and FeIII/II couples are +0.349 V and
+0.293 V vs. a [Fe(CN)6]3−/4− internal standard, respectively (see
Fig. S2, ESI†), i.e. the FeIII complex is stabilised by approxi-
mately 56 mV compared to the CuII complex. It is therefore
possible that any FeII formed at the cathode during electrolysis
reduces CuII to CuI. Alternatively, FeIII may oxidise S2− to S0 or
SO42−, which may in turn interact with the CuI ions, as well as
forming further FeII that may reduce CuII. No iron is present in
Published on 08 November 2019. Downloaded by Northwestern University on 1/3/2020 2:06:17 AM.
either the CuS or Cu2S systems, hence the copper species
retain the higher oxidation state.
For copper chloride salts, speciation in 1ChCl:2U and
1ChCl:2EG is similar. However, after anodic dissolution of cov-
ellite in 1ChCl:2U, a mixed ligand complex formed, containing
1.4(3) × O-/N-donor and 1.9(4) × Cl− ligands. This O-/N-donor
ligand is likely to be based on urea, or decomposition products
such as ammonia. The absence of multiple scattering signals
around 4–5 Å would tend to suggest that urea is not directly co-
ordinated to the copper ions, as was seen for CrCl3·6H2O:urea
Type 4 eutectics.54 Spectra for chalcocite were not recorded
due to low Cu concentrations. From comparison of UV-vis
spectra, we propose that the speciation is the same as for covel-
lite. Intriguingly, linear combination fitting of the XANES data
suggests that copper ions are present in a ratio of 30% CuI and
70% CuII (see Fig. S3, ESI†).
Table 2 shows that when urea was present in the DES, FeCl2
and FeCl3 form O- or N-donor complexes. In these cases, the
coordinating ligand is probably urea, due to multiple scatter-
ing signals around 4–5 Å. Interestingly, the fitted parameters
and XANES data indicates that FeIII-species are present in both
cases (see Fig. S4, ESI†). If Fe species formed from the anodic
dissolution of chalcopyrite behave in the same way, the use of
1ChCl:2U should result in different speciation than 1ChCl:2EG
and hence electrochemistry. As discussed previously, 1ChCl:2U
was too viscous to be a viable solvent for bulk electrodissolu-
tion of chalcopyrite. Therefore, in order to retain these altered
speciation properties whilst reducing viscosity and increasing
conductivity, a solution of 1ChCl:2EG with 20 wt% 1ChCl:2U
was used.
As EXAFS for the 1ChCl:Ox systems was not measured, the
UV-vis spectra were once again considered. By comparing the
unknown 1ChCl:Ox systems to the known 1ChCl:2EG and
1ChCl:2U systems, it can be seen that copper retains the tetra-
chloride speciation, whilst iron forms a completely different
Fig. 7 The composition of the deposit on five consecutive cathode plates from each experiment for direct electrowinning from chalcopyrite. Left:
1ChCl:2EG only, Middle: +20 wt% 1ChCl:2U, and Right: +20 wt% 1ChCl:1Ox.
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Paper
complex in each solvent (Fig. S5, ESI†). Although the specia-
tion behaviours of metal salts in DESs are not directly compar-
able to aqueous solutions, aqueous stability constants can still
be used to obtain an indication of which complex is most
likely to be dominant in DES media. In aqueous solutions, the
cumulative stability constants for the tetrachloride and trisoxa-
lato complexes at 25 °C are −1.26 and 18.49, respectively.55,56
The stability constant for the tetrachloride species in the DES
systems will naturally be higher than the aqueous value, given
the EXAFS data for iron chloride salts in 1ChCl:2EG, however
the difference between the stability constants is sufficiently
large that it is most likely that iron oxalate complexes domi-
nate in 1ChCl:Ox.
Bulk recovery of copper from chalcopyrite
A mixed DES system of 1ChCl:1.5EG:0.5U DESs has already
been applied to the treatment of electric arc furnace dust,
selectively recovering lead and zinc from a dust containing Pb,
Zn and Cd.36 By mixing DESs, a solvent with optimal viscosity
and metal solubility properties can be obtained. In the present
study, three DESs were tested for bulk leaching and recovery
experiments; neat 1ChCl:2EG, 1ChCl:2EG with 20 wt%
1ChCl:2U and 1ChCl:2EG with 20 wt% 1ChCl:1Ox. To check
that no H2S was generated during the experiment using the
20 wt% 1ChCl:1Ox system, a strip of lead acetate paper was
suspended above the experiment. No blackening of the paper
was observed, indicating that H2S is not generated from this
mixture.
For all systems, the Ni cathode in the cell (Fig. 1) was
replaced every 24 h and the composition of the material de-
posited on the cathode was determined. Fig. 7 shows that with
the 1ChCl:2EG system, the first electrowon deposit obtained
after 24 h was almost pure copper. This showed that the recov-
ery process is selective. However, with subsequent digestion
and plating, the iron content gradually increased while that for
copper decreased. The increasing iron content was coupled
with a corresponding increase of the oxygen content (but neg-
ligible sulfur), indicating the formation of iron oxides. The
addition of 20 wt% 1ChCl:2U improved the selective recovery
of copper, with a maximum of 3.4 at% Fe impurity on one
plate. The best results were obtained from the 20 wt%
1ChCl:1Ox system, where only 1.7 at% Fe was present on the
final plate, with Cu averaging 99% over the five plates. By alter-
Green Chem., 2019, 21, 6502–6512 | 6509
 View Article Online

Paper Green Chemistry

Table 3 Composition of the precipitate remaining in cell after release of copper ions which could be recovered from solution.
electrowinning No surface passivation or formation of elemental sulfur was
observed during these experiments. The main copper species
System Cu/g Fe/g S/g
present in 1ChCl:2EG after dissolution of chalcocite and covel-
1ChCl:2EG 0.22 0.53 0.76 lite was [CuCl4]2−. In the solution formed from chalcopyrite, a
+20 wt% 1ChCl:2U 0.45 0.19 0.04
mix of CuII and CuI species were formed instead, potentially
+20 wt% 1ChCl:1Ox 0.33 0.033 0.06
due to generation of reducing FeII species at the cathode. In
1ChCl:2U, copper had a mixed chloride/O- or N-donor coordi-
Published on 08 November 2019. Downloaded by Northwestern University on 1/3/2020 2:06:17 AM.

nation, potentially altering electrochemical behaviour.

ing the HBDs present, the speciation (and hence complex
Electrochemical oxidation of sulfide minerals resulted in
stability) of the Fe complexes are changed, without affecting
the formation of sulfate in solution and avoided the generation
Cu deposition. This in turn alters the reduction properties of
of SO2 or H2S, except when 1ChCl:1Ox was used as a neat DES.
the Fe species in solution.
Copper could be electrowon from chalcopyrite in the three
The water content of the solvent can affect speciation,
DESs tested with varying purities. In 1ChCl:2EG the proportion
however according to De Vreese et al.57 and Li et al.58 the
of iron increased over the course of the experiment. With the
amount of water necessary to cause a significant change in
addition of 20 wt% 1ChCl:2U, copper purity increased, and the
copper speciation in DES or ILs is in the region of ca. 40 wt%
best selective recovery of copper (99 at%) was with 20 wt%
H2O. As we only anticipate a maximum of ca. 5–10 wt% H2O
1ChCl:1Ox solution. This is inferred to be due to changes in
even from very long exposure to atmospheric moisture or
iron speciation and electrochemical behaviour between the
damp minerals, the only impacts expected would be a decrease
three liquids, resulting in different electrodeposition con-
in solution viscosity, and corresponding increase in mass
ditions being required for Fe. From analysis of the liquids left
transport properties.59 This lack of water sensitivity is impor-
after the experiment and their precipitates, it can be shown
tant for industrially relevant processes, where the need for
that electrolytic dissolution alone does not selectively separate
rigidly controlled atmospheres are undesirable.
the two metals, and that selectivity is instead obtained at the
After the neat 1ChCl:2EG experiment, the electrolyte sur-
cathode during electrowinning. This demonstrates that DESs
rounding the cathode turned brown, with a darker brown pre-
can be used to selectively recover metals from solution by
cipitate at the bottom of the container. The solutions contain-
changing solute speciation and hence redox properties.
ing 20 wt% 1ChCl:2U and 1ChCl:1Ox instead turned green and
grey/blue respectively, with a green/brown bottom precipitate.
The high sulfur content in the 1ChCl:2EG bottom precipitate
(Table 3) compared to the other systems suggests that either
Conflicts of interest
elemental sulfur or iron sulfides are present in the deposit. There are no conflicts to declare.
XRD analysis indicated that the precipitates were composed of
amorphous material, with some unreacted chalcopyrite
present in the 20 wt% 1ChCl:1Ox solution. Addition of Acknowledgements
aqueous BaCl2 solution to the remaining liquid produced a
cloudy precipitate for all of the DESs used, indicating that The authors would like to thank the German Research
some of the sulfur forms sulfate, as it would in an aqueous Foundation (DFG grant FR 3458/2-1) and the NERC Minerals
solution. As either urea or oxalic acid is added to 1ChCl:2EG, Security of Supply (SoS) grant NE/M010848/1 Tellurium and
the total mass of bottom precipitate decreases. The mass of Selenium Cycling and Supply (TeaSe) for funding, and the
copper remains roughly constant but that of iron decreases sig- European Synchrotron Radiation Facility for beamtime. The
nificantly. This shows that additives can significantly change authors would also like to thank Dr Philip Bird for carrying
solubility and selectivity for extraction. out the Zeiss analysis and Vicky Ward, the Geological Curator
Subsequent to the completion of these experiments, it was at Leicester, for helping source the samples.
discovered that carboxylic acid-based DESs degrade via an This paper is dedicated to Syahrie Angarra for his hard work
esterification mechanism between the acidic HBD and the OH- during his Masters project, who sadly passed away after com-
group of the choline chloride.60 This esterification will natu- pleting his Masters dissertation. He will always be remembered
rally change the properties of the employed DES over time and as a warm-hearted colleague.
will be of significance for the reuse and recyclability of these
solvents.
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