Journal of Solid State Electrochemistry (2020) 24:1291–1304

https://doi.org/10.1007/s10008-020-04613-2

ORIGINAL PAPER

Mechanistic analysis of anodic dissolution of cobalt in alkaline

glycine solution
Twinkle Paul 1 & Ramanathan Srinivasan 1

Received: 14 December 2019 / Revised: 17 April 2020 / Accepted: 21 April 2020 / Published online: 11 May 2020
# Springer-Verlag GmbH Germany, part of Springer Nature 2020

Abstract
The kinetics of dissolution of Co in alkaline glycine solution under anodic conditions was investigated. Potentiodynamic
polarization and electrochemical impedance spectroscopic (EIS) data of Co dissolving in 0.1 M glycine solution at pH 10 were
acquired. At low overpotentials, in the active region, the polarization current increases with potential, whereas at high
overpotentials, in the passive region, it decreases with potential. Co surface exposed to the alkaline glycine solution was
characterized using scanning electron microscopy and x-ray photoelectron spectroscopy, and based on the binding energies of
the deconvoluted peaks, oxides, hydroxides, and Co-glycine complexes were identified as the likely species present on the
surface. Impedance data was subjected to electrical equivalent circuit analysis, and a circuit with three Maxwell elements was
found to model the faradaic impedance. Polarization and EIS data were also analyzed in the framework of mechanistic analysis,
and a mechanism with four adsorbed intermediates is proposed. The proposed model captures the salient features of the
polarization and EIS results.

Keywords Cobalt anodic dissolution . Complexing agent glycine . Chemical mechanical planarization . Potentiodynamic
polarization . Electrochemical impedance spectroscopy . Reaction mechanism

Introduction industry, Co CMP has been extensively studied, with slurries

Due to its low resistivity as well as super adhesive and electro-
migration resistance properties, Co has emerged as a promis-
ing replacement for adhesion or barrier layer for Cu metalli-
zation and Cu interconnect metal in integrated circuits [1–5].
Chemical mechanical planarization (CMP) of Co is one of the
important processes in the semiconductor industry, and it uti-
lizes synergic effects of chemical dissolution along with me-
chanical abrasion in a slurry to remove excess Co.
Electrochemical mechanical polishing (ECMP) is a process
in which the removal rate is enhanced by applying anodic
potential to the metal, and ECMP offers better lower
defectivity [6]. By virtue of its importance in semiconductor
Electronic supplementary material The online version of this article
(https://doi.org/10.1007/s10008-020-04613-2) contains supplementary
material, which is available to authorized users.
* Ramanathan Srinivasan
srinivar@iitm.ac.in
1
Department of Chemical Engineering, Indian Institute of
Technology-Madras, Chennai 600036, India
containing various organic chemicals such as glycine [1, 3, 7],
citric acid, oxalic acid, tartaric acid [8], lysine, proline, argi-
nine [9], acetate [10], and an EDTA derivative [11], while
ECMP of Co in KOH [12] and H2O2-based systems [13] has
been reported.
Glycine is a simple amino acid which can complex with Co
[1]. Co CMP with glycine is usually conducted in alkaline
environment [3, 9, 10, 14, 15] although acidic slurries have
also been evaluated [1]. Lu et al. [1] evaluated Co CMP in
glycine-based slurries at pH 3 and proposed that Co2+ ions are
chelated by glycine. Jiang et al. [3] studied Co CMP in slurries
with H2O2 and 0.1 M glycine at pH 8 and suggested that
glycine forms a water-soluble Co(III) glycine complex during
CMP. He et al. [16] evaluated effect of inhibitors in glycine
solution for Co CMP application, at pH 8.5. Based on electro-
chemical quartz crystal microbalance studies, they reported
that glycine enhances Co dissolution and the dissolution rate
can be reduced by 1,2,4, triazole. In addition to Co CMP
applications, glycine has been employed as a complexing
agent in post-CMP cleaning of Co [2] and in Co electrodepo-
sition [17]. While ECMP of Co in KOH [12] and H2O2-based
systems [13] has been evaluated, ECMP of Co in glycine has
1292
not been reported. A clear understanding of anodic dissolution
of Co in glycine can help in development of Co ECMP pro-
cess in glycine-based systems.
Detailed mechanistic studies of Co anodic dissolution in
alkaline environment has been reported in literature, but main-
ly in bicarbonate/carbonate solutions [18–20]. Real et al. stud-
ied Co dissolution in carbonate/bicarbonate solution in the pH
range of 8.9–10.5, using polarization and EIS techniques, and
proposed a mechanism involving Co(OH)ad as an intermedi-
ate species and [Co(CO3)2]2−as the soluble product. Calderon
et al. [19, 20] investigated Co electrodissolution in carbonate/
bicarbonate media and proposed a reaction model involving
Co(HCO3)ads and CoO as intermediates, with [Co(CO3)2]2−as
the soluble product. Gallant et al. [21] analyzed cyclic volt-
ammogram of Co in bicarbonate/carbonate solution and
employed a deconvolution algorithm to assign the observed
peaks to various oxidation reactions. Based on the analysis,
formation of Co(CO3) and its subsequent dissolution as
[Co(CO3)2]2−was proposed as the reaction corresponding to
the first peak; formation of CoO and its subsequent dissolution
as Co2+ was assigned to the second peak, and the oxidation of
CoO to Co3O4 was assigned to the last peak. Ismail and
Badawy reported polarization, impedance, and XPS studies
of Co in KOH solution and proposed that surface would be
passivated by a film containing oxides and hydroxides [22].
According to their analysis, the inner layer of the film would
contain a mixture of Co(OH)2 and CoO, while the outer layer
would be made of Co(III) in the form of CoO(OH). Although
mechanistic analysis of Co in bicarbonate/carbonate alkaline
solutions and in KOH is available in literature, to the best of
our knowledge, there is no published report of detailed mech-
anism of Co dissolution in glycine solution, and in particular
in alkaline conditions.
In this work, we investigate Co dissolution in alkaline so-
lution in presence of glycine, using potentiodynamic polariza-
tion and electrochemical impedance spectroscopy (EIS). The
surface was characterized using scanning electron microscopy
(SEM) and x-ray photoelectron spectroscopy (XPS). A multi-
step reaction mechanism with four adsorbed intermediates
was proposed. Based on the proposed model, polarization
and EIS data were simulated to match with the experimental
results. From the model and best fit kinetic parameters, the
fractional surface coverage of the intermediate species at an-
odic potential was estimated.
Experimental
A standard three electrode cell, with a 5 mm diameter Co as
working electrode (Alfa Aesar, 99.95% purity), saturated sul-
fate electrode (Hg/Hg2SO4 with saturated K2SO4, SSE) as
reference electrode and Pt mesh (Alfa Aesar, 99.99% purity)
as counter electrode was used. Commonly used reference
J Solid State Electrochem (2020) 24:1291–1304
electrodes such as Ag/AgCl or saturated calomel electrode
can lead to chloride contamination of the solution, which
can lead to pitting corrosion of Co [23] and hence SSE was
employed as reference electrode in this work. The electrolyte
contained 0.1 M glycine, with 1 M NaClO4 (99.9%, Loba
Chem) as supporting electrolyte. Analytical grade chemicals
from Merck were used in Milli-Q water of 18.2 MΩ cm resis-
tivity. The solution pH (10) was adjusted using 1 M NaOH.
Co electrode surface was polished using grit paper of increas-
ing fineness and final abrasion was performed with 3000 grit
paper and 0.3 μm alumina powder. Then, the electrode was
ultrasonicated in ethanol and rinsed in Milli-Q water. Before
each experiment, N2 was bubbled in the electrolyte for 10 min,
and the electrode was polarized at negative potential for 1 min
to reduce the native oxide.
PARSTAT 2263 (AMETEK, USA) electrochemical work-
station was used to conduct the electrochemical experiments.
The working electrode was rotated at 900 rpm using Pine
Instruments MSR since rotations at higher rpm yielded essen-
tially the same results. Initially, the open circuit potential
(OCP) of Co in the electrolyte was monitored as a function
of time and all the other experiments were performed only
after stabilization of OCP. Polarization experiments were per-
formed by starting at OCP and scanning the potential at
1 mV s−1 in the anodic direction. EIS experiments were per-
formed by superimposing an ac perturbation of 10 mV ampli-
tude on a given dc bias. The perturbation frequency was var-
ied from 20 kHz to 0.1 Hz at 7 frequencies per decade, which
were logarithmically spaced. At lower frequencies, the data
was noisy and not reproducible, and hence are not shown. All
the EIS data presented in this work were validated using linear
KKT software [24] .
The surface morphology of the electrode was characterized
using SEM (Hitachi S4800) and the surface oxidation state
was investigated using PHI Versaprobe III using Al Kα x-
ray source at 1486.7 eV. The data was corrected using the
value of C1s peak at a binding energy of 284.8 eV and
Shirley approximation was used for background removal.
XPS Peak 4.1 software (R.W.M. Kwok) was used to de-
convolute the XPS peaks. Potential-pH diagram of Co in gly-
cine was prepared using the freely available software
Medusa® [17, 25, 26]. To generate the potential-pH diagram,
the concentration of Co2+ species in solution was fixed at
10−5 M and the concentration of total glycine was fixed at
0.1 M. A database containing various complexes was gener-
ated using the Hydra® component of the software, and from
the database, the potential pH diagram was generated using
the Medusa interface. Medusa software has been used in lit-
erature to create potential-pH diagrams of Cu in phosphate-
buffered saline [27], to generate chemical equilibrium species
of Co in glycine solution [28], Cu-NH3-citrate bath [29], and
Ti in alkaline solution [26] and to identify passive region in Zn
in alkaline solutions [30].
J Solid State Electrochem (2020) 24:1291–1304 1293

Results and discussion

Polarization results

The OCP of Co in 0.1 M glycine solution at pH 10, as a

function of time is shown in Fig. 1. It is clear that the OCP
is very stable and is − 1054 mV vs. SSE. All the experiments
were conducted after the working electrode was held at OCP
for 5 min. Figure 2 shows the potentiodynamic polarization of
Co in glycine solution. The experimental results, shown as
continuous line, were reproducible within 2%. Mechanistic
analysis predictions, explained later, are shown as dashed
lines. The experimental results show that the current increases
with potential initially, and after reaching a maximum of ~
5.2 mA cm−2 at − 844 mV vs. SSE, the current decreases with
potential. The region where current increases with potential is
the active dissolution region, and the region where it decreases
with potential can be considered as passive region. It is to be
noted that the term passive is not used to indicate that the
Fig. 2 Potentiodynamic polarization curve of Co, rotated at 900 rpm, in
surface is protected from dissolution; here, it only implies that
0.1 M glycine solution at pH 10, with 1 M NaClO4 as supporting
the current decreases with potential in this region, while in electrolyte. The potential of the working electrode was scanned at
fact, dissolution continues to occur. In bicarbonate/carbonate 1 mV s−1 . Experimental data are shown as continuous line and
solutions at pH 8.9, Co is reported to exhibit a similar trend of mechanistic model results are shown as dashed line. The dc potentials,
where EIS data were acquired, are marked as open diamonds
initial increase in current followed by a decrease in current
with potential, due to a passivation process [19].
Beyond − 660 mV vs. SSE, the current increases with po- dissolution requires modeling of the 3D film, along with the
tential, and in this region, transpassive dissolution occurs. In movement of the vacancies and ions through the film [33].
this region, the surface would normally be covered by a three- The investigations in this paper are limited to analyze the
dimensional film, and metal dissolution would occur by the processes in the potential region before transpassive dissolu-
movement of ions through the film, under a large electric field tion occurs.
[31]. Electrochemical machining of Co is in fact conducted in
transpassive dissolution region [32]. Analysis of trans passive
Potential pH diagram

Glycine is known to form complexes with Co in acidic neutral

Fig. 1 Open circuit potential vs. time of Co held in solution with 0.1 M
glycine and 1 M NaClO4 supporting electrolyte at pH 10
and alkaline conditions and enhance the dissolution rate [1,
17, 34]. Potential pH diagrams, also known as Pourbaix dia-
grams, are valuable in identifying solubility and stability of
metal species in the solution of interest [35]. The potential pH
diagrams of Co in water [36] and ammonia [32] solutions are
available in literature. The potential pH diagram for Co in
glycine solution was constructed using Medusa® software
and is presented in Fig. 3. The concentration of glycine used
was 0.1 M and the activity of Co2+ was chosen to be 10−5. In
water at alkaline pH, Co would be passivated by oxides or
hydroxides [36], but glycine reduces the stability region of
these passivating films (Fig. 3), and soluble complexes can
be formed at pH 10. Specifically, [Co(gly)3]− complex is the
likely form, in the potential region where the EIS data were
acquired (open diamonds in Fig. 3). The potential pH diagram
facilitates identification of the most stable forms of the com-
plexes, although the detailed mechanism of formation and
kinetics cannot be obtained from it.
1294
Fig. 3 Potential-pH diagram of Co-glycine-water system, for a dissolved
Co activity of 10−5 M and glycinate species activity of 0.1 M. The poten-
tials at which EIS data (shown in Fig. 6) were acquired are marked as
open diamonds
Surface characterization
Figure 4a shows the SEM image of Co dissolving in 0.1 M
glycine solution in the active region (held at − 914 mV vs.
SSE for 30 min). The surface appears rough, due to enhanced
dissolution of the metal in the active region. On the other
hand, the SEM image of Co dissolving in the same solution
in the passive region (− 704 mV vs. SSE) exhibits relatively
less roughness, as seen in Fig. 4b. This is likely because the
surface is protected by a film in the passive region. The sample
surface was also characterized using XPS and the results of O
1s and Co 2p are presented in Fig. 5. Markers are the exper-
imental results, the continuous lines are the model fits, and the
colored areas are the individual, de-convoluted peaks. XPS is
an ex situ technique, and the sample may be oxidized during
transfer from the electrochemical cell to the XPS chamber.
Since the sample was held under passivating conditions, the
sample would be covered with a passive film and further sur-
face modifications are less likely. In Fig. 5a, between a bind-
ing energy of 775 eV and 790 eV, four peaks at 778.3, 779.1,
780.7, and 786.7 eV corresponding to Co 2p3/2 levels were
resolved. The first peak can be attributed to metallic Co
(2p3/2), and the last peak to Co2+ (2p3/2Sat), while the two at
779.1 and 780.7 eV could arise from Co2+ or Co3+ (2p3/2) or a
mixture of them.
The XPS peak of metallic Co 2p3/2 is reported to occur at
778.3 eV in one study [37] and at 778.5 eV in another study
[38], and thus, the peak observed at 778.3 eV in this report can
be assigned to metallic Co 2p3/2. The binding energy of Co
2p3/2 in Co3O4 was reported to occur at 779.3 eV [39],
J Solid State Electrochem (2020) 24:1291–1304
(a)
(b)
Fig. 4 Scanning electron micrographs of Co held in a solution with 0.1 M
glycine and 1 M NaClO4 for 30 min in a active region (− 914 mV vs.
SSE), b passive region (− 704 mV vs. SSE)
779.5 eV [40], and 779.6 eV [41, 42]. In addition, organic
complexes of Co also show peak in this binding energy range.
To the best of our knowledge, there is no report on XPS peaks
of Co-glycine complex. Escard et al. analyzed the XPS peaks
of certain organometallic compounds and reported that
[(CH3)4N]4Co(NCSe)6 exhibits a peak at 779.0 eV [43].
Barber et al. analyzed (π C 2 H 5 ) 2 Co and the peak at
779.3 eV was assigned to Co 2p3/2 [44]. It is possible that
the peak observed at 779.1 eV could arise from Co-glycine
complex or Co3O4 or from both, since if the peaks from Co-
glycine complex and Co3O4 are very close, then they cannot
be separated easily.
Haber and Ungier analyzed Co, CoO, and Co3O4 and
assigned the peak at 780.4 eV to Co2+ 2p3/2 in CoO [39].
Another study reported that Co2+ adsorbed on α-FeOOH at
pH 10 exhibited a peak at 780.6 eV, while Co(OH)2 exhibited
a peak at 781 eV [45]. The peak observed at 780.7 eV in this
study can be due to cobalt oxides or hydroxides. Literature
indicates that a satellite peak at 786.4 eV was observed for
Co(OH)2 and a satellite peak at 786.1 eV was observed for
J Solid State Electrochem (2020) 24:1291–1304
Fig. 5 XPS data of Co held in
0.1 M glycine and 1 M NaClO4 (a)
for 30 min in passive region (−
0.704 V vs. SSE) a Co 2p, b O1s.
Experimental results are shown as
points, and de-convoluted com-
ponents are shown as dashed lines
with colored area
(b)
Co2O3 [46]. The peak seen at 786.7 eV in the present study is
the satellite peak of either Co(OH)2 or Co2O3.
From a binding energy of 790 eV to 805 eV, three more
peaks at 793.4, 794.8, and 797.4 eV corresponding to Co 2p1/2
levels are resolved. The energy difference of the doublet peaks
of Co (2p3/2) and Co (2p1/2) was 15.1 eV, which matches well
with that reported in literature [46]. Alstrup et al. reported that
metallic Co 2p1/2 peak occurs at 793.6 eV, and the peak at
793.3 eV in this work is assigned to metallic Co. The binding
energy of Co 2p1/2 in Co3O4 is reported to occur at 794.5 eV
[42], or 794.8 eV [47] and 795.2 eV [48]. Hence, the peak at
794.8 eV in Fig. 5a can be assigned to Co3O4 (2p1/2). The peak
at 797.4 eV in Fig. 5a of this study is also close to reported
value of Co3O4 (2p1/2) peak (797.8 eV) in the literature [48].
The O 1s spectrum (Fig. 5b) shows a peak 530.1 eV and
another at 531.9 eV. Wagner et al. analyzed several metal
oxides using XPS and Auger and reported that the O1s peak
of Co3O4 occurred at 530 eV. In another study, the O1s peak of
Co3O4 was reported to occur at 529.7 eV and that of Co2O3 at
529.9 eV [49]. The peak seen in this work at 530.1 eV would
1295
arise from Co2O3 or Co3O4. The peak at 531.9 eV is likely to
arise from cobalt glycine complex, since oxygen in another Co
organic complex (Co with 3-Br-2,4-pentanedione) is reported
to exhibit a peak at 531.9 eV [50, 51]. Based on the XPS
analysis of the Co held at − 704 mV vs. SSE in glycine solu-
tion, one can conclude that the Co surface analyzed contains a
mixture of Co oxides, hydroxides, and organo-metallic
complexes.
Impedance results
Electrochemical impedance spectroscopy is an established
technique and is widely used to study a variety of electro-
chemical phenomena [52, 53]. EIS data were acquired by
superimposing an ac perturbation on certain dc bias values
which are denoted by diamond markers in Fig. 2. The results
are shown as complex plane plots in Fig. 6. The markers
represent the experimental data while the lines represent
EEC model predictions, explained later. Figure 6a shows that
at − 984, − 914, and − 864 mV vs. SSE, in the active region, at
1296
Fig. 6 Complex plane plots of
impedance spectra acquired in a
the active region and b passive
region. Experimental results are
shown as markers and electrical
equivalent circuit (EEC) model
results using the circuit given in
Fig. 7 are shown as lines
least two loops are visible to the naked eye. The high-
frequency loop impedance would arise from the parallel ele-
ments of double layer and the charge transfer resistance, and
the mid- and low-frequency loops would correspond to the
faradaic process influenced by the relaxation of adsorbed
intermediates.
Figure 6a also shows that when the dc bias is increased
from − 984 to − 914 mV vs. SSE, the diameter of the high-
frequency loop diminishes, indicating that the charge transfer
resistance decreases with potential. There is no clear and sig-
nificant difference in the high-frequency loops observed at dc
bias values of − 914 mV and − 864 mV vs. SSE. When the dc
bias is changed from − 984 to − 914 mV vs. SSE, the low-
frequency limit of impedance decreases, but then, the dc bias
is decreased further to − 864 mV vs. SSE, and the low-
frequency limit of impedance increases significantly.
Figure 6b shows the results in the passive region, and it is
seen that the low-frequency impedance values tend toward the
negative real axis. At high frequencies, a capacitive loop cor-
responding to the double layer in parallel with the charge
transfer resistance is observed. Beyond this point, at mid fre-
quencies, the real part of impedance increases with a decrease
in frequency, suggesting a capacitive behavior. This is marked
by the arrow in Fig. 6b. At lower frequencies, the data points
move toward the second quadrant in the complex plane with a
decrease in frequency, indicating that lower frequency values
J Solid State Electrochem (2020) 24:1291–1304
(a)
(b)
would show negative resistance. It is well known that in the
passive region, low-frequency negative resistance would be
observed in the impedance spectra [54–56]. As the polariza-
tion curve exhibits a decrease in current with an increase in
potential, the sinusoidal current response to low-frequency ac
potential would exhibit a phase difference of 180 °, which
would manifest as negative resistance.
Electrical equivalent circuit analysis
The impedance data presented in Fig. 6 were modeled using
circuit shown in Fig. 7, where Rsol is the solution resistance, Rp
is the polarization resistance, and (Ri,Ci) (i = 1, 2, and 3) are
the Maxwell pairs. It is possible to use Voigt or ladder circuits
to represent the faradaic impedance equally well since they are
degenerate [57]. The best fit parameters are listed in Table 1
and the values in parenthesis are the corresponding standard
errors. The standard error is relatively large for Maxwell ele-
ments and small for the CPE parameters, Rsol and Rp. The
high-frequency loop is actually a depressed semi-circle and
was modeled using a constant phase element rather than a
simple capacitor. Initially, a circuit with one or two Maxwell
elements was evaluated, but the fit was poor for most of the
spectra. Only the data at − 984 mV vs. SSE could be modeled
with two Maxwell elements and the remaining data were
modeled with three Maxwell elements. The CPE exponent n
J Solid State Electrochem (2020) 24:1291–1304 1297

Fig. 7 Circuit employed to model

experimental EIS data in Fig. 6.
The data at 0.07 V vs. OCP were
modeled using only two Maxwell
elements, while all other data
were modeled using three
Maxwell elements. The
polarization resistance Rp was
allowed to hold negative values to
model the data in the passive
region

is less than 1 indicating that the surface is rough. CPE behav-
ior could arise from a variety of causes including non-
uniformity in chemical or structure, variation along the surface
or perpendicular to the surface (e.g., heterogeneous film),
electrode porosity etc. [58, 59], and in case of Co dissolving
in glycine solutions, it is likely caused by the surface
roughness.
The value of Rsol remains more or less a constant (2.2 ±
0.1 Ω cm2) for all the EIS data reported here. The low-
frequency limit of faradaic impedance is the polarization re-
sistance, and Table 1 shows that the variation of Rp with the dc
bias is non-monotonic. In the passive region, since the polar-
ization current decreases with potential (Fig. 2), the polariza-
tion resistance is negative, which is along the expected lines
[55, 60]. The standard errors in the Maxwell element values
are relatively larger, and more importantly, it is challenging to
obtain physical insights from these values. In addition, the
circuit model cannot be used to predict the potentiodynamic
polarization curve (Fig. 2). To understand the details of reac-
tions better, the polarization and EIS data were analyzed in the
framework of mechanistic analysis, as described below.
Reaction mechanism analysis
Initially, a three-step mechanism with two adsorbed interme-
diates viz. Co2þ 3þ
ads and Coads , described in Eqs. (1)–(3) was
evaluated. Here, ki (where i = A, -A, B, -B, C, D, and E) are
the rate constants of each step, with negative sign correspond-
ing to the reverse reaction. In the dissolution steps, the reverse
reactions are neglected since the dissolved species is carried
away from the interface. The rate constants of electrochemical
steps are assumed to have exponential relationship with po-
tential, while those of chemical steps are independent of

Table 1 Electrical equivalent circuit parameters, for Co dissolution in 0.1 M glycine solution at pH 10. The EIS data in Fig. 6 were modeled using the
circuit shown in Fig. 7. The values in parenthesis are the standard errors

DC bias (E) /mV vs. SSE − 984 − 914 − 864 − 784 − 704
Rsol/Ω cm2 2.3 (1%) 2.4 (1%) 2.4 (1%) 2.4 (2%) 2.4 (1%)
Q-Y0/× 10−4 Ω−1 Sn cm−2 3.9 × 10−4 (5%) 3.2 × 10−4 (2%) 3.1 × 10−4 (2%) 3.4 × 10−4 (11%) 3.0 × 10−4 (7%)
n 0.79 (1%) 0.80 (1%) 0.72 (4%) 0.77 (2%) 0.80 (2%)
Rp/Ω cm2 25.3 (1%) 18.6 (1%) 28.3 (2%) − 45.1 (8%) − 36.0 (4%)
C1/mF cm−2 0.3 (13%) 1.3 (20%) 2.1 (6%) 80.0 (6%) 65.3 (4%)
R1/Ω cm2 85.3 (3%) 45.2 (9%) 36.5 (5%) 15.4 (3%) 17.5 (6%)
C2/mF cm−2 0.1 (13%) 0.5 (9%) 16.1 (6%) 7.5 (15%) 10.0 (18%)
R2/Ω cm2 138.7 (12%) 66.2 (7%) 38.8 (5%) 24.7 (7%) 26.4 (8%)
C3/mF cm−2 – 4.7 (7%) 0.1 (16%) 47.8 (21%) 0.1 (20%)
R3/Ω cm2 – 72.5 (7%) 49.8 (7%) 37.6 (10%) 51.2 (8%)
χ2 9.7 × 10−5 9.3 × 10−5 2.0 × 10−4 4. 6 × 10−4 2.4 × 10−4
1298 J Solid State Electrochem (2020) 24:1291–1304

potential [60–62]. For the electrochemical reactions, the rate evaluated. Here, ki (where i = 1, − 1, 2, − 2, 3, 4, 5, − 5, 6, − 6,
constant can be expressed as k i ¼ k i0 ebi E where ki0 is the pre- 7, and 8) are the rate constants of each step. In addition, the
exponential factor of rate constant. The exponent is given by reverse reactions in the steps 5–8 are neglected. A pictorial rep-
bi ¼ mα iF
RT where m is the number of electrons transferred in the
resentation of the same is given in Fig. 8b. This mechanism has
step, αi is the transfer coefficient (0 ≤ αi ≤ 1), F is the faraday been employed earlier to describe the dissolution of Zr in acidic
constant, R is the universal gas constant, and T is the fluoride media [68]. The polarization trends and impedance spec-
temperature. tra of Zr dissolution process were qualitatively different from
those exhibited by Co dissolution in alkaline glycine solution.
The stable oxidation states of Zr are + 3 and + 4, whereas they are
kA
‐ + 2 and + 3 for Co. Nevertheless, the dissolution of each metal-
Co ⇄Co2þ
ads þ 2e ð1Þ solution combination needs not to proceed via a unique and
k ‐A

kB
distinct mechanism, and hence, this model was evaluated.
‐ Most likely, in the mechanism described in Fig. 8, the ox-
ads ⇄Coads þ e
Co2þ ð2Þ
3þ
k ‐B ides, hydroxides, or glycinates of Co(II) are described, respec-
kC tively, by Co2þ 2þ
ads−1 and Coads−2 , and those of Co(III) are de-
ads → Cosol
Co3þ ð3Þ
3þ
scribed by Coads−1 and Co3þ
3þ
ads−2 , although the exact identities
kD ‐
ads → Cosol þ e
Co2þ ð4Þ
3þ of these species are not known. The fractional surface cover-
kE age of the intermediates species Co2þ 2þ 3þ
ads‐1 ,Coads‐2 ,Coads‐1 , and
‐
ads þ Co → Coads þ Cosol þ 3e
Co3þ ð5Þ
3þ 3þ
Co3þads‐2 is given by θ1, θ2, θ3, and θ4, respectively. For the

It is worth noting that only forward reaction constants are
considered in steps given in Eqs. (3)–(5) for the sake of sim-
plicity since the concentration of dissolved Co species in the
solution is negligible. In a rigorous definition, the term mech-
anism would consist of elementary steps only, which means
that multi-electron transfer steps, or any step with an order
other than 1 or 2, cannot be part of a mechanism [61, 63,
64]. On the other hand, literature has also employed such
pseudo-elementary steps as part of detailed mechanistic de-
scription of an overall reaction [65, 66], and the kinetics of
such steps can still be described by an equation similar to
Butler-Volmer equation [67]. In this work, the more lenient
definition of mechanism is employed, and pseudo elementary
steps are included in the mechanism.
While the polarization data in the active region could be
modeled using Eqs. (1)–(3), the decrease in current with po-
tential in the passive region could not be captured by the
model, and hence, it was rejected. Next, the mechanism de-
scribed in Eqs. (1)–(4) was evaluated and it could model the
active and passive regions of the polarization curve, but the
EIS data could not be modeled satisfactorily with this mech-
anism (Supplementary Figs. S1–S3). Subsequently, another
four-step mechanism given by Eqs. (1)–(3) and (5) was also
evaluated. The step is Eq. (5) is known as catalytic step, and
this mechanism could match the polarization data well, but the
match between the model and experimental data of the imped-
ance spectra was poor.
Since three Maxwell elements were required to model the EIS
results, any mechanism chosen to describe the Co dissolution in
glycine should employ three or more intermediate species.
Therefore, the mechanism given in Fig. 8a, with four intermedi-
ate species viz. Co2þ 3þ 2þ 3þ
ads‐1 ,Coads‐1 ,Coads‐2 , and Coads‐2 , was
adsorbed intermediate species, Langmuir isotherm model
was invoked and mass transfer is assumed to be rapid. The
mass balance equations for a similar mechanism have been
described earlier for Zr dissolving in HF [68] and are summa-
rized below.
dθ1
Γ ¼ k 1 θV −k −1 θ1 −k 3 θ1 þ k −3 θ3 −k 7 θ1 ð6Þ
dt
dθ2
Γ ¼ k 2 θV −k ‐2 θ2 −k 4 θ2 þ k ‐4 θ4 −k 8 θ2 ð7Þ
dt
dθ3
Γ ¼ k 3 θ1 −k −3 θ3 −k 5 θ3 ð8Þ
dt
dθ4
Γ ¼ k 4 θ2 −k −4 θ4 −k 6 θ4 ð9Þ
dt
Here, θv is the fraction of surface with exposed bare metal,
given by θv = 1- θ1- θ2- θ3- θ4, ki and k‐i are the rate constants
of forward reaction and reverse reaction and those dependent
with potential for electrochemical steps. Γ(gamma) is the
available sites per unit area. The faradaic current is given by


ð2  fk 1 θV −k −1 θ1 þ k 2 θV −k −2 θ2 gÞþ
iF ¼ F ð10Þ
ðk 3 θ1 −k −3 θ3 Þ þ ðk 4 θ2 −k −4 θ4 Þ þ k 7 θ1 þ k 8 θ2
The steady-state fractional surface coverage values (θi,ss)
can be obtained by setting Eqs. ( 6)–(9) to zero
(Supplementary S4). The steady-state faradaic current (iF,ss)
can be calculated from Eq. (11).
i F;ss ¼ 3 F½ðk 5 þ k 7dc Þθ1ss þ ðk 6 þ k 8dc Þθ2ss  ð11Þ
The subscript ‘dc’ in the rate constants indicates that they
are evaluated at the dc potential Edc. The equations for the rate
J Solid State Electrochem (2020) 24:1291–1304 1299

Fig. 8 Proposed reaction (a) 2 e- Co

mechanism. a Equation. b 2 e-
k1
Pictorial representation k2
k-1
k-2
2+ 2+
Co ads-1 Co ads-2
k7 k8
e- e- e- e-
3+
Co sol
k3 k-3 k4 k-4

k5 k6

Co3+
ads-1 Co3+
ads-2

(b) Co3+
sol

Co3+
ads-2

Co3+
ads-1 2+
Co ads-2
2+
Co ads-1

constants and fractional surface coverage values can be ex- rearrangement of Eqs (6)–(9) and (10), the charge transfer
panded in Taylor series and truncated after the first two terms, resistance Rct can be written as
to linearize the equations. After linearization and


2½b1 k 1dc θVss −b−1 k −1dc θ1ss þ b2 k 2dc θVss −b−2 k −2dc θ2ss þ
R−1 ¼F ð12Þ
ct ðb3 k 3dc θ1ss −b−3 k −3dc θ3ss Þ þ ðb4 k 4dc θ2ss −b−4 k −4dc θ4ss Þ þ b7 k 7dc θ1ss þ b8 k 8dc θ2ss

and the Faradaic impedance (ZF) can be written as

2 3
dθ1
6 ð2k 1dc þ 2k −1dc þ 2k 2dc −k 3dc −k 7dc Þ þ 7
6 dE 7
1 Δi F −1 6 dθ 7
≃ ¼ Rct −F 6 ð2k 1dc þ 2k 2dc þ 2k −2dc −k 4dc −k 8dc Þ
2
þ 7 ð13Þ
Z F ΔE 6 dE 7
4 dθ3 dθ4 5
ð2k 1dc þ 2k 2dc þ k −3dc Þ þ ð2k 1dc þ 2k 2dc þ k −4dc Þ
dE dE
1300 J Solid State Electrochem (2020) 24:1291–1304

The total impedance ZTotal can be written as results are captured by the simulations. At − 984 mV vs.
Z Total ¼ Rsol þ QðjωÞ1n þZ −1 . SSE, the model predicts a capacitive loop at high frequen-
F

The expressions for the derivatives of fractional surface cies, another capacitive loop at mid frequencies, and a
coverage with potential are given in Supplementary S5. The third capacitive loop at low frequencies, as seen in Fig.
Matlab® programs employed to calculate the polarization and 9a. The match between simulated and experimental results
electrochemical impedance data can be obtained by contacting is good in the high- and low-frequency regions, and in the
the corresponding author. The best fit kinetic parameters are mid-frequency region, the match is relatively poorer. An
listed in Table 2. The dashed lines in Fig. 2 are the model examination of Fig. 9b and c shows that there again, the
predictions of the polarization curve, and it is seen that the match is good in the high- and low-frequency regions and
simulated results are in fairly good agreement with the exper- is poorer at the mid-frequency region.
imental results in the active and passive regions. Figure 10 shows the comparison of experimental imped-
Table 2 shows that the pre-exponents of the forward reac- ance data and reaction mechanism model results in the passive
tions are smaller than the pre-exponents of the corresponding region. At − 784 mV vs. SSE, the model matches the data in
reverse reactions, but the actual values of the rate constants the high frequency and low frequency ends well and in par-
depend on the potential and the rates at any given potential ticular, the tendency of the real part of impedance value to
depend on the corresponding rate constant as well as the frac- move towards negative values at low frequencies is modeled
tional surface coverage of the relevant species. Under steady- correctly. In the mid-frequency region, the capacitive behav-
state conditions, the reaction rates of the forward steps (ri for ior, as indicated by the arrow in Fig. 10a, is also captured,
the ith step) are always larger than the rates of the correspond- although the match between experimental and simulation re-
ing reverse steps. sults is not quantitative. Figure 10b also shows that the mech-
The mechanistic model predictions of impedance data, anistic simulation results match the salient features of the ex-
in the active region, are shown in Fig. 9. Although the perimental results and that the match is good in the high- and
mechanistic simulation results are not identical to the ex- low-frequency ends, while it is relatively poor in the mid-
perimental data, the major features of the experimental frequency region. The assumption of Langmuir isotherm
model may not be accurate and models such as Frumkin or
Temkin isotherm may offer a better description of the process,
but will also increase the complexity of the model. It may be
Table 2 Best fit
parameter values used to Parameter Units Value possible to obtain better fit at mid frequencies by replacing the
simulate the mechanistic Langmuir model with other isotherms and by increasing the
model results in Figs. 2, k10 mol cm−2 s−1 1.8 × 10−10 number of intermediates and the reaction steps, but the confi-
9, and 10, using the k20 5.7 × 10−09 dence in the results would be poorer and hence they were not
reaction mechanism k30 5.0 × 10−10
shown in Fig. 8 attempted [53].
k40 1.4 × 10−08 It should be noted that the match in the mechanistic analy-
k50 7.2 × 10−14 sis (Figs. 9 and 10) is not as good as that observed in EEC fit
k60 4.4 × 10−11 (Fig. 6), but in case of EEC, each spectrum is fitted indepen-
k70 1.1 × 10−15 dently, and the polarization data cannot be predicted by EEC.
k80 1.2 × 10−08 The solution resistance values and the double-layer capacitor,
k−10 4.8 × 10−09 modeled by CPE, were obtained from EEC. In addition, the
k−20 1.9 × 10−07 minimum number of adsorbed intermediates present in the
k−30 9.9 × 10−06 chosen mechanism was guided by the number of Maxwell
k−40 4.4 × 10−06 elements required to describe the faradaic impedance in EEC
b1 V−1 3.7 [62]. Although it is possible to extract the kinetic paramters
b2 10.7 from EEC element values, the process is more tedious than
b3 15.1 fitting the mechanistic model results to the experimental data,
b4 15.6 and hence, direct model optimization was employed in this
b7 32.3 work.
b8 21.3 In case of RMA, if we were to analyze only one impedance
b−1 − 14.4 spectrum, it could be matched very well (results not shown),
b−2 − 15.8 but the confidence in the model will be poor and it is not
b−3 − 15.2 possible to obtain physical insights reliably in both active
b−4 − 21.5 and passive regions. Therefore, the complete data set of im-
Г mol cm−2 4.2 × 10−8 pedance and the polarization data were fitted simultaneously
using the proposed mechanism.
J Solid State Electrochem (2020) 24:1291–1304
Fig. 9 Mechanistic model results
and experimental EIS data,
displayed as complex plane plots
in the active region a − 984 mV
vs. SSE, b − 914 mV vs. SSE, and
c − 864 mV vs. SSE.
Experimental results are shown as
open circles and mechanistic
model results are shown as filled
squares
Figure 11 shows the fractional surface coverage values of
Co2þ 3þ 2þ 3þ
ads‐1 ,Coads‐1 ,Coads‐2 , and Coads‐2 as predicted by the model.
Initially, near OCP, the surface is mostly bare metal, since
glycine would form soluble complex with Co. With an in-
crease in overpotential, the fractional surface coverage of
Co(II) species, as given by the sum of θ1 and θ2, increases,
reaches a maximum near − 805 mV vs. SSE, and then de-
creases to negligible values at − 650 mV vs. SSE. On the other
hand, the fractional surface coverage of Co(III) species is very
low near OCP and continues to increase, reaching almost full
coverage at − 650 mV vs. SSE. These predictions are in line
with the low current values observed at large anodic potentials
in Fig. 2. The fractional surface coverage values of the species
at a given potential are determined by the balance between
formation rate and the dissolution rate, and at large anodic
potentials, the oxide and hydroxide formation rate would be
higher, leading to passivation.
The rate of chemical and electrochemical dissolution of Co
in 0.1 M glycine solution at pH 10, predicted by the mecha-
nism in Fig. 8, are presented in Fig. 12. The steps in the legend
1301
(a)
(b)
(c)
of Fig. 12 refer to the steps shown in Fig. 8. The rate of each
electrochemical step is much larger than that of the corre-
sponding chemical step. Note that the ordinate is in logarith-
mic scale. The electrochemcial dissolution rate (step 8) in-
creases with potential, reaches a maximum at − 865 mV vs.
SSE, and then decreases with a further increase in potential.
This is essentially the product of the relevant rate constants,
which depend exponentially on potential, and fractional sur-
face coverage values of Co2þ ads‐2 , which exhibits a maximum
(Fig. 11). At large overpotenials, the increase in the values of
the rate constants of electrochemcial steps does not match the
decrease in fractional surface coverage of Co2þ ads‐2 with poten-
tial, and the net result is a decrease in electrochemcial disso-
lution rate beyond − 865 mV vs. SSE. On the other hand, the
chemical reaction rate constants are independent of potential,
and the chemical dissolution rate (step 6) follows the variation
of Co3þads‐2 species with potential faithfully and shows a con-
tinuous increase till − 650 mV vs. SSE.
The rate of other electrochemical dissolution (step 7) is
significantly smaller than step 8, and the rate of the
1302 J Solid State Electrochem (2020) 24:1291–1304

(a)

Fig. 11 Fractional surface coverage of bare Co and various adsorbed

intermediates of the proposed mechanism (Fig. 8), as a function of poten-
tial in 0.1 M glycine solution at pH 10

spectra are influenced by even minor reactions whose contri-

bution to the polarization data may be small. The proposed
mechanism describes the observed polarization and imped-
ance data satisfactorily and offers insights into the variation
of the fractional surface coverage of the intermediate species
and the dissolution rates as a function of potential. Impedance
alone cannot be used to identify the species present on the
surface, but as a versatile in situ technique, it can offer valu-
able insights into the physicochemcial processes occuring at
the electrode-electroltye interface. In conjuction with
potential-pH diagram and XPS results, mechanistic analysis
of polarization data and impedance spectra can be used to
identify the mechanism and the possible intermediate species.

(b)

Fig. 10 Mechanistic model results and experimental EIS data, displayed

as complex plane plots in the passive region; a − 784 mV vs. SSE and b −
704 mV vs. SSE. Experimental results are shown as open circles and
mechanistic model results are shown as filled squares

corresponding chemcial dissolution (step 5) is even smaller

Fig. 12 Chemical and electrochemical Co dissolution rates vs. potential
than that. The contribution of step 5 and step 7 to the polari- in 0.1 M glycine solutions at pH 10, as predicted by the reaction
zation data is minimal. The results also show that impedance mechanism model
J Solid State Electrochem (2020) 24:1291–1304
Conclusions
Anodic dissolution of Co in 0.1 M glycine solutions was in-
vestigated using potentiodynamic polarization and electro-
chemical impedance spectroscopy. Well-defined active and
passive dissolution regions are seen in potentiodynamic polar-
ization data. Impedance spectra acquired in the active and
passive regions were modeled using electrical equivalent cir-
cuit as well as mechanistic analysis. A mechanism with four
adsorbed intermediates, viz. two Co(II) and two Co(III) spe-
cies, which could be oxides, hydroxides, and glycine com-
plexes of Co, was proposed and fitted to the experimental data
to obtain the kinetic parameters. The presence of Co oxides,
hydroxides, and possible organo-metallic complexes was
identified by the analysis of XPS data. The proposed mecha-
nistic model predicts that the chemical dissolution rate would
increase with potential and saturate at large anodic
overpotential, whereas the electrochemical dissolution rate
would exhibit a maximum at intermediate overpotential and
would be small at small and large overpotentials.
Acknowledgments The authors thank the Department of Science and
Technology, India, for providing the SEM facility to the Department of
Chemical Engineering, Indian Institute of Technology Madras through
the FIST program, and Prof. B. Boukamp, U Twente, for the linear KKT
software.
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