Electronic Supplementary Material (ESI) for Green Chemistry.

This journal is © The Royal Society of Chemistry 2019

Direct Extraction of Copper from Copper Sulfide Minerals using Deep

Eutectic Solvents
Syahrie Anggara,a Francesca Bevan,a Robert C. Harris,a Jennifer M. Hartley,a,b Gero Frisch,b
Gawen R. T. Jenkin,c Andrew P. Abbotta*

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

E-mail: apa1@le.ac.uk;

Supplementary Information:
1.0 1.0
CuS CuFeS2 CuS
Cu2S
Cu2S CuCl CuCl2
CuCl
CuCl2 FeCl2 + CuCl
Absorbance
normalised

normalised
0.5
FeCl3 + CuCl
0.5

0.0
0.0
200 300 400 500 600 700 300 400 500 600 700 250 300 350 400 450 500
 / nm  / nm  / nm

Figure S1: UV-vis comparisons of Cu-species in 1ChCl:2EG (left), identification of species

in leached chalcopyrite (middle), and Cu-species in 1ChCl:2U (right).

0.5
E0(aq.) = E0(DES)
1ChCl:2EG Cu2+/+
1ChCl:2U Fe3+/2+

[Fe(CN)6]3-/4-
E0'(DES) / V

0.0

Cu+/0
-0.5

Fe2+/0
-1.0
-1.0 -0.5 0.0 0.5

E0'(aq.) / V

Figure S2: Graph showing the formal electrode potentials for copper and iron in 1ChCl:2EG
and 1ChCl:2U.
 CuCl2
CuCl
CuS

normalised x(E)
FT k2 (k)
k2 (k)

CuCl2
CuCl
CuS

2 4 6 8 10 12 0 1 2 3 4 5 6 8970 8980 8990 9000 9010 9020 9030

k / Å-1 r/Å Energy (eV)

Figure S3: EXAFS, Fourier transforms, and XANES of CuCl2, CuCl, and CuS in 1ChCl:2U.
In 1ChCl:2U the CuS is more closely related to CuCl than CuCl2.

FeCl2
FeCl3

FeCl2

normalised x(E)
FT k2 (k)

FeCl3
k2 (k)

2 3 4 5 6 7 8 9 10 11 12 0 1 2 3 4 5 6 7100 7110 7120 7130 7140 7150 7160

k / Å-1 r/Å Energy (eV)

FeCl2
FeCl3
normalised x(E)

FeCl2
FT k2 (k)
k2 (k)

FeCl3

2 3 4 5 6 7 8 9 10 11 12 0 1 2 3 4 5 6 7100 7110 7120 7130 7140 7150 7160

k / Å-1 r/Å Energy (eV)

Figure S4: EXAFS, Fourier transforms, and XANES of Fe chlorides in 1ChCl:2EG (top)
and 1ChCl:2U (bottom). In 1ChCl:2EG both species are tetrachloride, with different
oxidation states. In 1ChCl:2U both species are urea-complexed, with the same oxidation
states.
 10 1ChCl:Ox
1.5 1ChCl:Ox
1ChCl:2EG
1ChCl:2EG
1ChCl:2U
1ChCl:2U
8
Normalised absorbance

Normalised absorbance
1.0
6

4
0.5
2

0
0.0
200 250 300 350 400 450 500 250 300 350 400 450 500
 / nm  / nm

Figure S5: Normalised UV-vis spectra of CuCl2 (left) and FeCl3 (right) in the three different
DESs, showing that speciation remains similar for copper but changes substantially for iron.