Acta Materialia 236 (2022) 118111

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Acta Materialia
journal homepage: www.elsevier.com/locate/actamat

The overlooked mechanism of chalcopyrite passivation

Zihe Ren a,∗, Chihwei Chao a, Prashanth Krishnamoorthy b, Edouard Asselin b,
David G. Dixon b, Nelson Mora a
a
Jetti Services Canada, Vancouver, BC V6C 2X8, Canada
b
Department of Materials Engineering, The University of British Columbia, Vancouver, BC V6T 1Z4, Canada

a r t i c l e i n f o a b s t r a c t

Article history: Chalcopyrite (CuFeS2 ) is the world’s main source of copper. Electrification of the global economy will rely
Received 18 February 2022 on economically viable Cu dissolution from low grade chalcopyrite ores, but this process is particularly
Revised 27 May 2022
slow. The reason for this slow reaction has been in dispute for over 50 years. In this study, electrochem-
Accepted 21 June 2022
ical analysis showed that n-type chalcopyrite is in an accumulation state when immersed in electrolyte,
Available online 22 June 2022
not in a depletion state as is commonly assumed. A leaching test and surface analysis confirmed the for-
Keywords: mation of a Cu-rich surface layer during oxidative leaching. In addition, a similar leaching test on covellite
Chalcopyrite (CuS) showed leaching kinetics that were as slow as chalcopyrite. Ex-situ current-voltage analysis showed
Covellite that the Cu-rich (covellite-like) product layer on the surface of chalcopyrite was a p-type semiconductor.
Leaching Therefore, as leaching progresses, chalcopyrite transitions from a resistor to a diode. Three mechanisms
Passivation for slow dissolution of chalcopyrite in acidic ferric media are proposed based on these tests: 1. The dielec-
tric breakdown potential of chalcopyrite (0.7 V vs Ag/AgCl) is higher than what the ferric/ferrous redox
couple can provide (0.5 V). 2. A chemically stable covellite-like surface layer prevents further Cu dissolu-
tion. 3. Rapid formation of a p-n junction on the leached chalcopyrite surface hinders the electrochemical
process. We hypothesize that all three mechanisms together prevent the full dissolution of chalcopyrite
under oxidative conditions at ambient temperature.
© 2022 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

1. Introduction
Chalcopyrite (CuFeS2 ) is the most abundant Cu-bearing min-
eral, representing 70% of the known global copper reserve [1]. Hy-
drometallurgical extraction of Cu from chalcopyrite ore has been
hindered by the extremely slow chalcopyrite dissolution rate un-
der standard heap bioleaching conditions using acidic ferric sul-
fate media [2]. Although extensive studies have been carried out
for almost 50 years, the reasons for slow chalcopyrite dissolution—
especially in acidic ferric sulfate media—remain under intense de-
bate [2–5]. Currently, two hypotheses dominate the debate:
Hypothesis 1: During oxidation, a metal-deficient sulfide/
polysulfide product forms a passivation layer on the chalcopyrite
surface that prevents further dissolution.
Hypothesis 2: Chalcopyrite is an n-type semiconductor; there-
fore, it is intrinsically passive under anodic potentials due to the
depletion of charge carriers on its surface.
Hypothesis 1 is generally based on the assumption of a mech-
anism akin to metal passivation: the product layer acts like a pas-
sive layer that protects the bulk mineral from further electrochem-
∗
Corresponding author.
E-mail address: zren@jettiresources.com (Z. Ren).
ical corrosion. This theory was first proposed by Biegler and Swift
in 1979 where fresh chalcopyrite shows a small prewave when
anodically polarized (0.4 to 0.85 V vs SHE) [6]. It was shown in
1981 that the product of this prewave is a metal deficient poly-
sulfide and it slows the electron transfer [7]. Since then, a sig-
nificant amount of effort has been put into determining the na-
ture of this product layer [8–11], and the term “passivation” or
“passive layer” became widely used to describe the slow dissolu-
tion of chalcopyrite associated with this product layer [7–13]. On
the other hand, Hypothesis 2 is based on the argument that the
presence of a sulfide/polysulfide product layer does not mean it is
passivating and that the semiconductor properties of the bulk n-
type semiconductor are determinative. This theory was proposed
in 1988 by Crundwell when analyzing the semiconductor behavior
of chalcopyrite [14]. It was further argued that the so called “pas-
sive region” is a result of the slow supply of holes to the surface
which is due to the nature of the n-type semiconductor under an-
odic bias [5–16].
Research over the past 50 years has provided experimental evi-
dence to support both hypotheses. In the present work, we clarify
some misunderstandings surrounding Hypotheses 1 and 2 and pro-
vide new insights into the problem.

https://doi.org/10.1016/j.actamat.2022.118111
1359-6454/© 2022 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Z. Ren, C. Chao, P. Krishnamoorthy et al.
2. Method
2.1. XRD analysis
X-ray diffraction was performed on chalcopyrite and covel-
lite mineral samples. Pulverized mineral samples (75–106 μm)
were examined with a Bruker D8 diffractometer with Cu radiation
source. The diffractometer was set to run at 40 kV × 40 mA, with
step size of 0.1° and 1 s per step from 20 to 80°. Results are shown
in Appendix Fig. A1.
2.2. Leaching tests
For bioleaching tests, a pure natural chalcopyrite sample was
used. The mineral was pulverized and sieved to particle size be-
tween 75 and 106 μm. The chemical assay using multi-acid di-
gestion followed by inductively coupled plasma atomic emission
spectroscopy (ICP-AES) showed that the sample contained 33.7% Cu
and 28.7% Fe, which is close to the theoretical composition of pure
chalcopyrite (34.6% Cu and 30.4% Fe). Reagent grade CuS (99.99%
purity, Sigma Aldrich) was sieved to the same particle size as chal-
copyrite and was used in the leaching tests for comparison. The
lixiviant used in bioleaching experiments contained acidithiobacil-
lus ferrooxidans and 2.2 g/L of Fe3+ . The solution was adjusted to
pH = 1.7 by reagent grade 95 – 98% concentrated sulfuric acid.
Leaching tests were conducted in a 1 L bioreactor under ambient
conditions at a stirring speed of 500 rpm. A pulp density of 1 g/L
was used for both chalcopyrite and covellite leaching. Use of low
pulp density in leaching tests ensures minimal change to the solu-
tion matrix during the experiment. Copper and iron concentrations
were analyzed with ICP-AES.
2.3. Electrochemical analysis
Bulk chalcopyrite from the same source as that used in the bi-
oleaching tests was mounted in epoxy resin with electrical con-
tact provided on the unexposed side via conductive epoxy bonding
of the mineral with a copper wire. All chalcopyrite mineral elec-
trodes were prepared in an identical manner. All electrochemical
experiments were performed at room temperature using a VersaS-
TAT 4 potentiostat/galvanostat controlled by VersaStudio software.
A conventional three-electrode electrolytic cell was used for elec-
trochemical analysis. All electrode potentials in this study are re-
ported with respect to the Ag/AgCl reference electrode.
Two types of electrodes were used: electrodes passivated by
immersion in an active bioleach and electrodes passivated via elec-
trochemical potentiostatic polarization.
The bioleached chalcopyrite electrodes were prepared by sus-
pending the mineral electrode in the same leaching solution as the
bioleaching tests (Section 2.2) for 120 days at room temperature
to ensure passivation. During the bioleach-passivation process, the
lixiviant was continuously agitated at 300 rpm and the ORP was
maintained at around 750 mV (platinum ORP electrode, vs. 4 M
KCl, Ag/AgCl) by A. ferrooxidans. A uniform, dark blue colored sur-
face was formed on the chalcopyrite after bioleaching.
The electrochemically polarized chalcopyrite electrodes were
prepared by applying a voltage of 0.7 V vs Ag/AgCl for 2 h on the
mineral electrode suspended in acidic water (pH = 1.7). Concen-
trated sulfuric acid (reagent grade 95–98%) was used for pH ad-
justment for all experiments. A uniform, dark blue colored surface
was formed on the chalcopyrite after electrochemical polarization.
2.3.1. Open circuit potential analysis
Open circuit potential (OCP) analysis is used to determine the
potential range that a ferric/ferrous couple can provide. Two sets
of solutions were used in the analysis. The first set of solutions
2
Acta Materialia 236 (2022) 118111
contained 10 mM of total iron with ferric to ferrous mole ratios
of 0:10, 2:8, 5:5, 8:2 and 10:0. The second set of solutions con-
tained 100 mM total iron with the same range of mole ratios. All
solution matrices were adjusted to pH 1.7 with sulfuric acid. OCP
readings were obtained by equilibrating the freshly polished chal-
copyrite mineral electrode in the solution matrix for one hour.
2.3.2. Mott Schottky analysis
Mott Schottky (MS) analysis was performed on a freshly pol-
ished chalcopyrite mineral electrode. The test was conducted in
acidic water at pH 1.7 adjusted by H2 SO4 . MS analysis was con-
ducted over the scan range of 0.2 to 1.0 V vs Ag/AgCl with a step
size of 5 mV. For the data plotted in Fig. 1, the frequency was
3162 Hz and the amplitude was 10 mV.
2.3.3. Polarization analysis
Linear sweep voltammetry was used to reveal the I–V character-
istics of fresh and bioleached chalcopyrite samples. The electrolyte
used in the tests was DI water acidified by sulfuric acid to pH 1.7.
Tests were performed on the same mineral sample in two different
stages. In stage 1, the fresh surface was created by polishing the
mineral electrode with 1200 grit polishing paper. The linear sweep
test was then conducted immediately after polishing at a scan rate
of 2 mV/s up to 0.7 V with the solution agitated at 500 rpm. In
stage 2, the same sample was then immersed in bioleaching lix-
iviant for 120 days (same procedure as listed in Section 2.2) and
then analyzed under the same linear sweep test conditions. Results
are shown in Appendix Fig. A3.
2.3.4. EIS analysis
Two sets of electrochemical impedance spectroscopy (EIS) were
performed on freshly polished and electrochemically polarized
electrodes. The scans had frequency ranges from 1 to 10 kHz with
Vrms = 10 mV. Both sets of EIS analyses were performed in acidic
water (pH 1.7). Solutions were kept stagnant during all EIS mea-
surements. In the first set of experiments, a freshly polished chal-
copyrite electrode was used. The electrode was polarized for 0 to
3.5 h at 0.5 V vs Ag/AgCl with EIS analysis conducted after each
potentiostatic polarization. The purpose of this test was to confirm
the presence and the formation kinetics of a product layer when
a chalcopyrite electrode is polarized at the potential exerted by a
common lixiviant such as acidic ferric sulfate media but far below
the dielectric breakdown potential (0.7 V). A similar test was car-
ried out at 0.45 V for 120 h to further confirm the effect with the
results shown in Fig. A4. The second set of EIS analyses was car-
ried out with a polarized electrode (0.7 V for 2 h) under different
DC biases from 0.1 to 0.6 V. The other experimental conditions and
parameters were the same as in the first set.
2.4. Time-of-flight secondary ion mass spectrometry (TOF-SIMS)
analysis
For TOF-SIMS analysis, bulk chalcopyrite samples from the same
source were used. The electrode was first polished using 1200 grit
sandpaper and cut into two pieces to produce two comparable
mineral surfaces. The freshly polished piece was used as a standard
and was not exposed to solution – it was exposed to ambient air.
The other piece was suspended in a reactor containing bioleaching
lixiviant solution (Fe3+ = 2.2 g/L, pH 1.7, with acidithiobacillus fer-
rooxidans, agitation rate = 500 rpm). The tests were run at room
temperature for 240 h. Both samples were rinsed with deionized
water and acetone before TOF-SIMS analysis. TOF-SIMS measure-
ments were made with a PHI Trift V nano TOF-SIMS with Au ion
source at a sputter rate of approximately 2 nm per second. Analy-
sis was carried out using Au LMIG operated in bunched mode us-
ing the Au+ primary ion. The raster area of 100 μm × 100 μm was
Z. Ren, C. Chao, P. Krishnamoorthy et al. Acta Materialia 236 (2022) 118111

Fig. 1. (a) Potential range (shaded area) for the OCP of a fresh chalcopyrite electrode immersed in ferric/ferrous solution at pH 1.7 and 25 °C. Current density and capacitance
vs applied potential for freshly polished chalcopyrite plotted as (b) log(i) and 1/C2 and (c) i and C.

3
Z. Ren, C. Chao, P. Krishnamoorthy et al.
selected. Mass spectra were collected in the mass-to-charge (m/z)
range of 0–200 amu. Data were averaged over 5 different areas in
each sample. The copper to iron ratio in the leached sample was
normalized against a freshly polished sample assuming a Cu/Fe ra-
tio of 1 throughout the entire depth profile.
2.5. Ex-situ I–V analysis
Two chalcopyrite mineral electrodes were used in this study to
compare the diode properties of bioleached vs electrochemically
polarized samples. The bioleached sample was prepared by im-
mersing the mineral electrode in bioleaching lixiviant (the same
lixiviant as described in Section 2.2) for 120 days. The electro-
chemically polarized sample was prepared by applying a voltage
of 700 mV vs Ag/AgCl for 2 h on the mineral electrode suspended
in acidic water (pH 1.7). Prior to I–V analysis, all samples were
rinsed with DI water and acetone to remove water soluble and or-
ganic matter. I–V analysis was performed on a Keithley 2100 digital
multimeter with a scan range from –0.75 to +0.75 V. The connec-
tion was designed to analyze the passivated electrode as a diode.
Therefore the ‘high’ channel was connected to the surface of the
electrode and the ‘low’ channel was connected to the bulk. The
connection was made by covering the surface of the mineral elec-
trode with silver paste along with one end of a gold wire. In order
to minimize experimental error, the bioleached and electrochem-
ically polarized samples were analyzed first. After these measure-
ments, the silver paste was removed by acetone rinsing. The elec-
trode was subsequently polished over 1200 grit polishing paper to
expose fresh surface, and the freshly polished electrodes were an-
alyzed in the same way as described above.
3. Results
3.1. When fresh chalcopyrite meets the lixiviant
Fig. 1(a) highlights the ORP range that the ferric/ferrous re-
dox couple provides, which is also marked as the shaded area in
Fig. 2(b) for reference. Hence, when fresh (unreacted) chalcopyrite
meets acidic ferric sulfate lixiviant, the oxidation potential it may
“feel” lies in the range of 0.32 to 0.5 V vs Ag/AgCl. Electrochemi-
cal analysis was performed to investigate interactions between un-
reacted chalcopyrite and the electrolyte (deionized water acidified
with sulfuric acid to pH 1.7). The Mott-Schottky equation is used
to evaluate the flat band potential (EFB ) assuming the Helmholtz
layer capacitance CH is much larger than the space charge layer
capacitance CSC .
  1/2
1 1 1 1 2 kT
= + ≈ = E − EF B −
CTot CH CSC CSC eε ε 0 n 0 e than the bulk sample (Fig. A3).
where e represents the charge of an electron, ε the dielectric con-
stant of the semiconductor, ε 0 the permittivity of free space, n0 the
donor density, E the applied potential, EFB flat band potential, k the
Boltzmann constant, and T the absolute temperature.
Based on Fig. 1(b), the OCP was 0.25 V, and the EFB was 0.53 V.
The dielectric breakdown—where current (i) increased dramatically
and capacitance (C) was inflected—occurred at 0.7 V (Fig. 1(c)).
One of the most common assumptions in semiconductor elec-
trochemistry is that when n-type semiconductors reach equilib-
rium with an aqueous electrolyte, their bands generally bend up,
forming a depletion region. This assumption is usually valid since
most semiconductors have their conduction band edge above the
H2 /H+ couple and their valence band edge below the OH– /O2 cou-
ple. However, it is not correct for chalcopyrite: EFB (0.52 V) was
higher than OCP (0.25 V). This means that fresh chalcopyrite re-
mains in the accumulation state as long as the solution’s redox
4
Acta Materialia 236 (2022) 118111
potential is below 0.52 V (Fig. 1(b)). The potential for the fer-
ric/ferrous redox couple generally ranges from 0.32 to 0.5 V vs
Ag/AgCl (Fig. 1(a)). Therefore, fresh chalcopyrite immersed in acidic
ferric sulfate lixiviant is in the accumulation zone, not the deple-
tion zone as previously assumed [5,17] (Fig. 1(b,c)). In fact, the EFB
reported here is likely an underestimate because the Helmholtz ca-
pacitance was omitted [18]. This further confirms that the fresh
mineral is in the accumulation zone. Data from the literature
have shown similar behavior but no interpretation has been given
[13,16]. The dielectric breakdown potential is the boundary be-
tween the depletion and inversion zones. Clearly, the value mea-
sured here (0.7 V) is much higher than what the ferric/ferrous re-
dox couple can provide. This explains why fresh chalcopyrite dis-
solves slowly when it meets the commonly used acidic ferric sul-
fate lixiviant.
3.2. The nature of the surface product
One consensus between Hypotheses 1 and 2 is the preferential
dissolution of iron over copper when chalcopyrite is under oxida-
tive leaching. Previous work refers to the copper-rich/iron-deficient
surface layer as a covellite (CuS) or a covellite-like phase [13,14,19].
However, because this layer is less than 100 nm thick [20,21], no
detailed crystal structure has been resolved and characterization of
its electronic properties is generally confounded by bulk proper-
ties.
A leaching experiment was designed to demonstrate the forma-
tion of a copper-rich/iron-deficient surface layer under ferric leach-
ing conditions. Leaching of chalcopyrite had extremely slow disso-
lution kinetics: < 7% of the Cu was extracted in 200 h (Fig. 2(a)). In
addition, the dissolved Cu/Fe molar ratio was < 1, showing prefer-
ential dissolution of Fe over Cu. TOF-SIMS on leached chalcopyrite
showed that the Cu/Fe ratio was > 1 on the leached mineral sur-
face (Fig. 2(b)). The ORP change during the leaching is shown in
Fig. A2.
It is well documented that crystalline covellite (CuS) is one of
the most refractory copper sulfide minerals [22,23] and that it is
a p-type semiconductor [24,25]. Previous work suggests that in
acidic ferric sulfate media, raising the temperature is the only ef-
fective means to increase Cu extraction from covellite [26]. Con-
sidering the compositional similarity between the Cu-rich layer
on chalcopyrite and pure covellite, leaching tests with pure crys-
talline covellite were performed under the same conditions as the
chalcopyrite leaching test (Fig. 2(a)). Covellite had almost identical
leaching kinetics as chalcopyrite. In addition, after a 120-day fer-
ric leach, the corrosion potential was higher for a bulk chalcopy-
rite sample (0.264 V) than for a freshly polished chalcopyrite sam-
ple (0.236 V), indicating that the surface product was more “noble”
3.3. The formation and effect of a p-n junction
The electrochemical and leaching test results converge and sup-
port our final proposed mechanism: the copper-rich, covellite-like
layer is a p-type semiconductor, leading to the formation of a p-
n junction since the bulk chalcopyrite is an n-type semiconductor.
Thus, as leaching progresses, the mineral transitions from a resis-
tor to a diode. This mechanism was verified with a simple ex-situ
current-voltage analysis. The current density vs voltage curve of a
chalcopyrite specimen leached for 120 days in acidic ferric media
measured outside the electrolyte showed typical diode properties
whereby the current dramatically increased above the knee poten-
tial of 0.5 V (Fig. 3(a)). In comparison, the freshly polished chal-
copyrite mineral behaved as a resistor with a linear increase in
current density with voltage. A second chalcopyrite specimen po-
Z. Ren, C. Chao, P. Krishnamoorthy et al. Acta Materialia 236 (2022) 118111

Fig. 2. (a) Copper recovery from chalcopyrite and covellite and dissolved Cu/Fe molar ratio during chalcopyrite bioleaching, (b) Cu/Fe molar ratio in the surface layer of the
leached chalcopyrite sample. TOF-SIMS image inserted.

5
Z. Ren, C. Chao, P. Krishnamoorthy et al.
Fig. 3. Current density vs bias voltage measured at solid state for chalcopyrite mineral after (a) 120-day bioleaching and (b) 2 h electrochemical polarization at 0.7 V vs
Ag/AgCl.
larized at the dielectric breakdown potential (0.7 V vs Ag/AgCl) for
2 h showed similar diode properties (Fig. 3(b)).
With confirmation of the presence of the p-n junction, further
characterization of the surface product and the junction proper-
ties in electrolyte was carried out using electrochemical impedance
spectroscopy (EIS). The first set of EIS experiments was designed to
demonstrate the electrochemical properties of the product layer as
well as its formation kinetics. EIS analysis on chalcopyrite, elec-
trochemically polarized at 0.5 V vs. Ag/AgCl for 0 to 3.5 h, is
shown in Fig. 4. Since the Nyquist plots showed only one semi-
6
Acta Materialia 236 (2022) 118111
circle (Fig. 4(a)), a simple Randles circuit was used to model the
interface with a resistor in parallel with a capacitor. A constant
phase element (Q) was used to model the complex capacitive be-
havior as a whole to avoid overfitting since several possible capac-
itive interactions contribute to the total capacitance (Fig. 4(c)). All
fitting parameters are shown in Table 1. The capacitance C is back-
calculated from Q using the following equation [27,28]:
(Q∗RCT )1/n
C=
RCT
Z. Ren, C. Chao, P. Krishnamoorthy et al. Acta Materialia 236 (2022) 118111

Fig. 4. Nyquist (a) and Bode (b) plots for EIS measurement on chalcopyrite mineral electrode polarized at 0.5 V vs Ag/AgCl for 0 to 3.5 h in acidic water at pH 1.7 and 25 °C.
(c) shows the equivalent circuit and the possible capacitances involved. CH : Helmholtz capacitance, Cn-s : junction capacitance between unreacted n-type chalcopyrite and
electrolyte, Cp-s : junction capacitance between p-type surface product and electrolyte. Cp-n : junction capacitance between surface product and bulk mineral (d) calculated
charge transfer resistance (RCT ) and capacitance based on the fitting of equivalent circuit.

Table 1 Table 2
Fitting parameters for the first set of EIS tests (Polarized at 0.5 V for 0– Fitting parameters for the second set of EIS tests (polarized at 0.7 V for
3.5 h before EIS analysis at OCP). 2 h before EIS analysis under DC bias from 0.1 to 0.6 V).

Time(Hour) RS ( cm2 ) CPE(S sn cm–2 ) n Rct ( cm2 ) DC bias (V) RS ( cm2 ) CPE(S sn cm–2 ) n Rct ( cm2 )
0.0 142 8.56E-05 0.85 5575 0.1 2278 1.41E-04 0.50 14,642
0.5 140 4.67E-05 0.87 7748 0.2 2197 1.21E-04 0.51 13,953
1.0 142 4.46E-05 0.87 8009 0.3 2114 9.78E-05 0.56 15,265
1.5 142 4.32E-05 0.87 8196 0.4 2309 7.02E-05 0.57 13,308
2.0 143 4.31E-05 0.87 8261 0.45 2269 7.72E-05 0.55 12,033
2.5 141 4.3E-05 0.87 8341 0.5 2347 8.12E-05 0.53 10,590
3.0 140 4.23E-05 0.88 8207 0.6 2239 8.10E-05 0.51 8842
3.5 142 4.34E-05 0.87 8551

The effect of polarization time at 0.5 V vs Ag/AgCl on the fitted
charge transfer resistance RCT and calculated capacitance is plot-
ted in Fig. 4(d). Note that the term “charge transfer resistance” has
been used conventionally to describe the resistance a charge car-
rier encounters when it moves from electrolyte species to the elec-
trode. In this case, since the electrode is a diode, RCT also includes
the resistance that a charge carrier overcomes when it crosses the
p-n junction.
The second set of EIS experiments was designed to reveal the
impact of the p-n junction on the system. Chalcopyrite mineral
electrodes were first polarized for 2 h at 0.7 V vs Ag/AgCl in or-
der to form a uniform and stable p-type product layer before fur-
ther analysis. The range of DC bias applied during EIS analysis was
chosen to be 0.1–0.6 V in order to cover both cathodic and an-
odic sides, which simulates forward and reverse bias at the p-n
junction, respectively. With similar semicircles in the Nyquist plots
shown in Fig. 5(a) as in Fig. 4(a), the same equivalent Randles cir-
cuit was used to model the interface between the polarized min-
eral and the electrolyte. The experimental results are shown in
Fig. 5 with fitted parameters shown in Table 2. Based on the fitting
results, RCT and capacitance are calculated and plotted in Fig. 6.
4. Discussion and conclusion
Similar to oxide passive layers or organic protective coating lay-
ers on metals, the depletion region at a p-n junction has its major-
ity charge carriers depleted, resulting in insulating behavior, which
hinders electrochemical reactions. Therefore, although it is not ac-
curate to apply the passivation mechanism of metals to the be-

7
Z. Ren, C. Chao, P. Krishnamoorthy et al. Acta Materialia 236 (2022) 118111

Fig. 5. (a) Nyquist and (b) bode plot for polarized electrode under different DC bias.

havior of a covalent compound [29,30] such as chalcopyrite, Hy- In the present case, for an n-type semiconductor, the formation
pothesis 1 remains largely correct when describing the chemi- of a p-type layer on its surface leads to the formation and ex-
cal nature and the combined effect of the product layer. Fig. 4(d) pansion of a depletion region. Thus, the increase of product layer
shows the increase of impedance and the decrease of capacitance area/thickness and associated depletion region also results in in-
after polarization at 0.5 V, which simulates the common oxida- creased impedance and decreased capacitance. The total capaci-
tive leaching conditions. This behavior is similar to metal with tance between the solid-liquid interface can be expressed as:
a metal-oxide passivation layer or organic coating layer, where a
thicker passive layer or more intact organic coating layer generally 1 1
CTot = ≈ Csc = Cn−s +
leads to increased impedance and decreased capacitance [31,32]. 1
+ 1 1
+ 1
CH Csc C p−s C p−n

8
Z. Ren, C. Chao, P. Krishnamoorthy et al.
Fig. 6. Effect of p-n junction on (a) current, charge transfer resistance and (b) capacitance under different DC biases. (c) and (d) describe the response of a p-n junction as a
working electrode under forward (cathodic) and reverse (anodic) bias. All tests were carried out in acidic water at pH 1.7 and 25 °C.
where CH is the Helmholtz capacitance in the liquid phase and CSC
is the space charge capacitance in the solid phase. Since CH >>
CSC , CSC is usually used to represent the total capacitance [33,34].
Fig. 4(d) also reveals the kinetics of the formation of the surface
product layer as the most drastic change in impedance and ca-
pacitance occurs within the first 30 min of polarization. This sug-
gests that the capacitance contribution from unreacted chalcopy-
rite and the electrolyte junction (Cn-s ) is rapidly overtaken by the
contribution from the product layer. Due to the lack of informa-
tion such as band structure or carrier density in the product layer,
a detailed calculation cannot be performed at this stage. However,
the decrease of total effective capacitance has clearly reflected the
decrease of carrier density since
Q
C=
V total effective capacitance is observed with increasing DC bias for
The second set of EIS experiments further elucidated the in-
teraction between the bulk and the surface layer as well as the
impact of the p-n junction. Fig. 6(a) shows that RCT remains con-
stant at the cathodic side and decreases dramatically when the DC
bias enters the anodic side. The measured current density is also
consistent with the change of RCT . Since charge transfer resistance
is inversely proportional to the charge transfer rate, this behavior
suggests that the electrochemical oxidation of bulk chalcopyrite to
the surface product is more favorable than the reverse (reduction)
reaction [35,36].
To further evaluate the impact of the junction on the system, it
is important to review the fundamental properties of p-n junctions,
especially the change of the junction capacitance under different
bias voltages. For the p-n junction, it is well known that the appli-
cation of reverse bias increases its depletion width and therefore
9
Acta Materialia 236 (2022) 118111
decreases its junction capacitance:
 2ε ε  N + N   12
r 0 A D
w= (Vbi − V )
q NA ND
εr A
Cj =
w
where w is the depletion width; ε r is the relative dielectric per-
mittivity of the semiconductor; ND and NA are the carrier density
for donors and acceptors; Vbi is the build-in potential and V is the
applied potential; Cj is the junction capacitance; A is the area of
the junction interface between p- and n-type semiconductors.
The response of total effective capacitance to the applied DC
bias also provides insight into the influence of the p-n junction
on the electronic properties of the mineral. In Fig. 6(b), a drop in
the polarized chalcopyrite mineral. This trend is the same as the
expected response of a p-n junction capacitance under increased
reverse bias, indicating that the p-n junction capacitance has the
dominant role in the total effective capacitance. In comparison, if
the junction capacitance between the p-type product layer and the
solution matrix (Cp-s ) were to dominate, then an increase in the to-
tal effective capacitance would have been observed because p-type
semiconductors enter the accumulation state under anodic poten-
tial, leading to an increase in their junction capacitance [37]. Note
that the effect of the p-n junction will be more pronounced in the
early stages of reaction since the product layer’s thickness is only
at the atomic scale. As a result, the entire p-type layer on the sur-
face can be fully depleted. Therefore, due to the lack of charge car-
riers, the ability of the mineral surface to act as the platform for
electrochemical reactions will be significantly hindered. This phe-
Z. Ren, C. Chao, P. Krishnamoorthy et al. Acta Materialia 236 (2022) 118111

nomenon is what has heretofore been referred to as passivation. It slow dissolution of chalcopyrite in acidic ferric media is not caused
is also interesting to note that, with the increase of DC bias, both by one, but rather by three mechanisms combined:
RCT and capacitance decreased. This unique behavior distinguishes
1. The dielectric breakdown potential for bulk chalcopyrite is ap-
chalcopyrite from metals since passivated metals exposed to dif-
proximately 0.7 V vs Ag/AgCl, which is higher than what the
ferent external conditions (such as acid concentration) usually lead
ferric/ferrous redox couple can provide (∼0.5 V).
to opposite trends for RCT and effective capacitance [38,39]. As for
2. Preferential dissolution of iron over copper generates a stable
metals, water uptake in the breached passive/coating film is the
surface product that greatly resembles covellite in its chemical
main contributor to effective capacitance [31]. In general, although
composition, electronic properties, and reaction kinetics.
the fundamental mechanism of chalcopyrite passivation is different
3. The formation of a p-type surface layer on n-type bulk chal-
from the passivation/coating of a metal, our finding that the prod-
copyrite is fast and changes the mineral from resistor to diode.
uct layer has a p-type nature and the leached material is a diode
The depletion region of the p-n junction hinders the electro-
still provides additional mechanistic support for Hypothesis 1.
chemical process and slows the dissolution reaction.
On the other hand, Hypothesis 2 is correct in stating that slow
chalcopyrite dissolution is due to it being intrinsically passive, but
Declaration of Competing Interest
this hypothesis has heretofore relied on an incorrect rationale. Ac-
cording to Fig. 1, the intrinsic passivity of chalcopyrite comes from
The authors declare that they have no known competing finan-
its high dielectric breakdown potential, not from the mineral being
cial interests or personal relationships that could have appeared to
an n-type semiconductor. Hypothesis 2 is also correct when relat-
influence the work reported in this paper.
ing the low dissolution rate to the formation of a depletion zone,
but again, the underlying rationale is incorrect. The depletion zone
Acknowledgment
is not the result of mineral reaching electrolyte: it results from the
formation of a p-n junction between the p-type surface product
The authors would like to thank Jetti Resources, Mitacs (Accel-
and the n-type bulk mineral.
erate and Elevate), BCIC Ignite, NSERC, and NRCan – Clean Growth
In summary, the surface layer generated from acidic ferric
Project for funding this research; Mr. Tae Kyong John Kim for his
leaching of chalcopyrite is a Cu-rich, iron-deficient compound that
great assistance with time-of-flight secondary ion mass spectrome-
resembles covellite in many ways: both are copper sulfides, both
try; Dr. Cathy Liu for her useful discussion on electrochemical anal-
are p-type semiconductors, and both have slow dissolution rates in
ysis; and Dr. Zenan Jiang for her useful discussion on semiconduc-
acidic ferric sulfate media. Our ferric leaching tests, ex-situ current
tor properties.
density vs voltage tests, electrochemical analysis, and surface anal-
ysis help to clarify some of the previous misunderstandings. The
Appendix.

10
Z. Ren, C. Chao, P. Krishnamoorthy et al. Acta Materialia 236 (2022) 118111

Fig. A1. XRD diffraction pattern of (a) Chalcopyrite and (b) Covellite.

11
Z. Ren, C. Chao, P. Krishnamoorthy et al. Acta Materialia 236 (2022) 118111

Fig. A2. Recorded ORP during the bioleaching of chalcopyrite and covellite. ORP is measured with ORP probe with platinum rings. The colored region suggests the possible
ORP range. With the same total iron, 100% ferric give the ORP at ∼750 mV as upper limit and 100% ferrous at ∼380 mV as lower limit.

Fig. A3. Polarization analysis on freshly polished and bioleached Chalcopyrite.

12
Z. Ren, C. Chao, P. Krishnamoorthy et al. Acta Materialia 236 (2022) 118111

Fig. A4. Nyquist (a), bode (b), and capacitance (c) plots of chalcopyrite mineral electrode polarized at 0.45 V for 120 hours.

13
Z. Ren, C. Chao, P. Krishnamoorthy et al.
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