D808 Journal of The Electrochemical Society, 165 (16) D808-D812 (2018)

0013-4651/2018/165(16)/D808/5/$37.00 © The Electrochemical Society

Iron Electrodeposition from Fe(II) Ions Dissolved in a Choline

Chloride: Urea Eutectic Mixture
Tu Le Manh,1,2,z E. M. Arce-Estrada,2 I. Mejı́a-Caballero,1 E. Rodrı́guez-Clemente,1
W. Sánchez,2 J. Aldana-González,1 L. Lartundo-Rojas,3 M. Romero-Romo, 1,∗
and M. Palomar-Pardavé 1,z
1 Universidad Autónoma Metropolitana-Azcapotzalco, Departamento de Materiales, Av. San Pablo 180 Col.
Reynosa-Tamaulipas, C.P. 02200 Ciudad de México, Mexico
2 Instituto Politécnico Nacional, ESIQIE, Departamento de Ingenierı́a en Metalurgia y Materiales, UPALM Ed. 7,
C.P. 07738 Ciudad de México, Mexico
3 Instituto Politécnico Nacional, Centro de Nanociencias y Micro y Nano Tecnologı́as, Av. Luis Enrique Erro S/N,
U.P. Adolfo López Mateos, Zacatenco, México D.F., 07738, Mexico

In this work, the Fe electrodeposition and nucleation and growth mechanisms onto a glassy carbon electrode from a choline
chloride-based deep eutectic solvent (DES) were studied using electrochemical techniques and surface characterization techniques
(SEM, EDS, and XPS). The current density transients were characterized by the strong effect of the induction-time during the Fe
electrodeposition process. A model comprising 3D nucleation and diffusion-controlled growth that considers the induction-time
offset was proposed and validated to analyze and explain the Fe nucleation and growth mechanism on the glassy carbon electrode.
Kinetic parameters of Fe nucleation and diffusion-controlled growth such as the nucleation rate, A, the number density of active
sites, N0 , the diffusion coefficient, D, as well as induction-time were determined. Iron electrodeposit follows an electrochemical
aggregative growth mechanism and was constituted by particles of Fe(0) and a mixture of FeO, Fe2 O3 and Fe(OH)3 .
© 2018 The Electrochemical Society. [DOI: 10.1149/2.0561816jes]

Manuscript submitted November 9, 2018; revised manuscript received November 30, 2018. Published December 11, 2018.

Electrodeposited iron is widely used for numerous applications Experimental

due to its desirable physical properties, its low cost,1 and magnetic
properties.2,3 The iron electrodeposition from aqueous electrolytes has
been extensively studied in the literature.1–5 It is well known, that the
use of aqueous media generates many technological problems and
environmental concerns,6–8 while the choline chlorine (ChCl)-based
deep eutectic solvent (DES)7–12 offers more advantages, including
better deposit quality obtained compared with that of the conven-
tional aqueous media. Despite this fact, only few approaches have
been done on the Fe electrodeposition from the DES. Böck et al.,13
have shown the electrodeposited Fe films from Fe(III) using the DES
formed by ChCl: urea onto copper substrates at 100◦ C, where they
focused on the impact of the current density on the layer thickness,
cathodic current efficiency and surface morphology of the deposited
iron films. Afterwards, in a recent work by Miller et al.,14 relating the
Fe electrodeposition with high Fe(II) and Fe(III) concentrations from
a DES based on ChCl: Ethylene glycol for flow batteries, they found
that physical properties of the electrolytes and the nature of the elec-
troplated iron are greatly influenced by electrolyte composition; for
solutions containing a Cl:Fe ≥ 4:1 molar ratio, the iron species such
as [FeCl4 ]− and [FeCl4 ]2− are dominant and when Cl:Fe < 4:1, the
ethylene glycol forms complexes with iron, although these could alter
the Fe electrodeposition mechanism.14 However, a thorough insight
into the Fe nucleation and growth mechanism from the DES has not
been reported yet.
Recent works15–18 have shown through electrochemical techniques
(cyclic voltammetry, CV, and chronoamperometry, CA) that when the
system is under a diffusion-controlled regime, the metal electrodeposi-
tion from the DES occurs by 3D nucleation mechanism, which could
be analyzed either by Scharifker and Mostany (SM)19 or Palomar-
Pardavé et al.,20 models.
This paper focuses on the Fe eletrodeposition, nucleation, and
diffusion-controlled growth mechanisms from a choline chloride-
based DES. Parameters of interest such as the nucleation frequency,
A, the number density of active sites, N0 , and the diffusion coeffi-
cient, D, were determined to assess the electrodeposition kinetics.
The surface deposit and elemental analyses were performed by field
emission scanning electron microscopy (FESEM), energy dispersive
spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS).
∗ Electrochemical Society Member.
z
E-mail: letuprofesor@gmail.com; mepp@correo.azc.uam.mx
Reactants and electrolyte preparation.—A mixture of choline
chloride and urea in a 1:2 molar ratio was prepared at 90◦ C to obtain
the DES, which was magnet stirred: the previously dried iron chloride
salt (50 mM FeCl2 ) was dissolved in the DES under stirring for 12
hours, thus forming the electrolyte. Details of the DES preparation
have been reported in the previous works.15–17 The electrochemical
experiments with the Fe(II)-DES system were carried out under pro-
tection of a N2 gas atmosphere covering the DES surface. All reagents
used were analytical grade from Sigma-Aldrich. The water content of
the Fe(II)-DES system was experimentally measured by Karl Fischer
coulometric titration (using a Titrino Coulometer, model 756 from
Metrohm), giving less than 0.1%.
Electrochemical experiments.—The iron nucleation and growth
mechanisms onto a glassy carbon electrode from DES were studied
through electrochemical methods such as CV and CA. These tests
were performed in a water-jacketed cell comprising three electrodes,
using a Potentiostat/Galvanostat PAR, Model 263A, coupled to the
Powersuite software running on a PC to facilitate experimental control
and data collection. The electrochemical cell was composed of a
glassy carbon electrode (GCE), with 0.1963 cm2 surface area as the
working electrode, a graphite bar and a silver wire as counter and
quasi reference electrode (QRE), respectively. The GCE surface was
polished with diamond spray down to 0.25 μm and washed in ethanol
using ultrasonic equipment during 30 minutes, and finally rinsed with
acetone in order to remove residual particles.
Physicochemical characterization.—The surface morphology of
the Fe deposited onto GCE from DES was characterized by a field
emission SEM JEOL 7000. The elementary analysis of the iron sur-
face deposit was determined by EDS and its composition by means
of X-ray photoelectron spectroscopy (XPS). The depth profiling in-
volved intermittent argon ion beam etch of 1 keV during 40 s. XPS
measurements were conducted on a ThermoFisher Scientific K-Alpha
Spectrometer with Al Kα (1487 eV). The vacuum in the analyzing
chamber was kept at10−9 mbar during data collection. The 400 μm
spot size X-ray beam was set in two pass energy modes of 200 and 20
eV, respectively. The analysis of the photoelectron spectra on differ-
ent regions located on the samples’ surfaces were collected and stored
in an interfaced personal computer, using Thermo Avantage V5.938
software.

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 Journal of The Electrochemical Society, 165 (16) D808-D812 (2018) D809

0.0005
a) 0.0012

0.0000 -1.06
0.0010
-1.04
-2

-0.0005 0.0008
j / Acm

-2
-1.02

j / Acm
-0.0010 0.0006 -1.00

-0.98
0.0004 -0.96
-0.0015
-0.94

0.0002 -0.92
-0.0020
-1.6 -1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4 0.6
0.0000
E/V 0 5 10 15 20 25 30 35 40

0.005 t/s

b) Figure 2. Experimental current density transients recorded during the iron

electrodeposition onto the GCE from the system DES/50 mM FeCl2 , at 70◦ C,
at the potentials indicated in V.
0.004
-2
- jcp / A cm

temperature (K), R is the universal gas constant (J mol−1 K−1 ), c0 (mol

0.003 cm−3 ) is the Fe(II) bulk concentration, D (cm2 s−1 ) is the diffusion
coefficient of Fe(II) ions.

Potentiostatic study.—Based on potentials range where Fe nu-

0.002
0.12 0.14 0.16 0.18 0.20 0.22 0.24 0.26
1/2 -1 1/2
v / (V s )
Figure 1. a) Cyclic voltammograms recorded in the systems: GCE/50 mM
FeCl2 dissolved in DES (blue line) and GCE/DES (red line). The potential
scan started at 0.18 V in the negative direction at 15 mVs−1 . b) Cathodic peak
current density (jcp ) as a function of the scan rate, v1/2 , where the markers ( )
correspond to the experimental data and the line to the linear fit (-j /A cm−2 =
0.0227 (A cm−2 /V1/2 s−1/2 ) v1/2 − 0.0009 (A cm−2 )).
Results and Discussion
Potentiodynamic study.—Figure 1 shows a voltammogram
recorded on the GCE from 0.05 M Fe2+ in the DES at 70◦ C. A typical
loop for Fe nucleation process is observed at potentials of −1.10 and
−0.82 V. There is a clearly defined reduction peak located between
potentials −1.2 and −1.0 V in the forward scan. The increase in the
current density after the reduction peak could be related to the DES
decomposition reactions as has been explained in the literature.7,12,15
In the backward scan, the peak located between the potentials range of
−0.8 and 0.4 V is associated with the oxidation of Fe phase previously
formed on the GCE during nucleation and growth mechanisms.
To assess the behavior of the Fe electrodeposition regime, the peak
current density (Jpc ) was plotted as a function of the square root of
the scan rate (v1/2 ) as depicted in the Figure 1 inset. This reveals
the linear dependence of the Jpc − v1/2 plot, which indicates that the
Fe nucleation onto the GCE from the DES occurred by a diffusion-
controlled mechanism, since it is in agreement with Berzins-Delahay
equation,21 see Eq. 1, and supported by similar results reported in
previous works15–17 dealing also with metals deposition from DES.
0.6105(z F)3/2 c0 D 1/2 1/2
j pc = v [1]
(RT )1/2
where z is the total number of electrons transferred during the overall
electrochemical process, F is the Faraday constant, T is the absolute
cleation occurs given by the voltammogram shown in Figure 1,
the chronoamperometric technique was employed to investigate the
Fe nucleation and growth mechanisms onto GCE from the DES.
Figure 2 depicts the experimental current density transients associ-
ated with the Fe nucleation and growth mechanisms onto the GCE, at
different potentials.
It is clear from the j-t plots shown in Figure 2 the formation of cur-
rent maxima followed by asymptotic current decay due to the growth
of metallic nuclei (new phase) on the GCE. To establish whether the
experimental current density transients could be analyzed by the SM
model19 or not and distinguish which nucleation and growth mecha-
nism they follow (instantaneous vs. progressive nucleation), the ex-
perimental data, normalized through their respective current maxima
(tm , jm ), were compared with theoretical plots using Eqs. 2 and 3 for
instantaneous and progressive nucleation, respectively.22
 2  −1    2
j t t
= 1.9542 1 − exp −1.2564 [2]
jm tm tm
 2  −1    2  2
j t t
= 1.2254 1 − exp −2.3367 [3]
jm tm tm
The form of the j-t plots of Figure 2 also indicates that the experi-
mental electrochemical responses are delayed by a so called induction-
time,23,24 t0 , that corresponds to the aggregation of primary nanoclus-
ters onto larger entities, which may grow at later stages.25 The t0 value
is significantly large at low applied potential (–0.92 V), but decreases
as the potential increases. To illustrate the effect of t0 on the current
density transients, a comparison between the experimental normalized
curve and the theoretical one with and without the induction-time off-
set is shown in Figure 3.
It can be noticed in Figure 3a that without any compensation for
t/tm ≤ 0.8 and t/tm ≥ 2 the experimental plot is below the zone limited
by the plots of Eqs. 2 and 3 (under the progressive curve), while the
peak within this time range follows the behavior described by the
SM model.19 However, it cannot work properly in its classic form.
This verified the need to consider the induction-time effect to make
feasible the use of the SM model on the experimental j-t plot analysis.
Solving this problem, Rigano et al.,24 demonstrated that the time

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 D810 Journal of The Electrochemical Society, 165 (16) D808-D812 (2018)

1.0 1.0
a) b)
0.8 0.8

0.6 0.6

2
2

(j / jm)
(j / jm)

0.4 0.4

0.2 0.2

0.0 0.0
0 1 2 3 4 5 6 7 8 9 10 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
t / tm t / tm

Figure 3. Comparison of the non-dimensional plots of the experimental current density transients (blue color) shown in Figure 2 with the theoretical ones for
instantaneous (green) and progressive (red) nucleation at −1.04 V a) without induction offset, see Eqs. 2 and 3, and b) with induction-time compensation, see
Eqs. 4 and 5.

scale offsetting can be performed by defining t = t − t0 . Applying this such as A, N0 , D, and t0 were determined, see Table I. The increasing
methodology, Eqs. 2 and 3 can be transformed in: tendency of the AN0 product confirms the validity of Eq. 6 to describe
 2      2 the Fe nucleation and growth mechanism occuring on the GCE sur-
j t − t0 −1 t − t0 face. Furthermore, t0 also decreased with increasing applied potential
= 1.9542 1 − exp −1.2564
jm tm − t0 tm − t0 as previously expected.
[4]
Induction-time determination.—Although the influence of the
 2        2 induction-time on the Fe nucleation and growth kinetics is previously
j t − t0 −1 t − t0 2
= 1.2254 1 − exp −2.3367 identified, it is not a straightforward determination. Two methods were
jm tm − t0 tm − t0 applied to estimate t0 as follows. First, t0 was determined by randomly
[5] selecting values within the time range (sufficiently large) t = 1 to
After the induction-time compensation using Eqs. 4 and 5, the nondi- 10 s with an increment t = 0.001 s that give the best-fit of j-t plots
mensional experimental j-t plot now falls expectedly in the validity to Eq. 6, see Table I.
zone and lies on the progressive nucleation curve (Figure 3b). Second, following the idea proposed by Rigano et al.,24 the rising
The nondimensional analysis results suggest that the current den- portions of the experimental j-t plots are useful since they contain a
sity transients shown in Figure 2 could be described through SM linear behavior within the time range defined by t0 and t before the
model19 only when the induction-time effect is appropriately included. 3D nucleation peak (see Figure 5). Therefore, a simple linear fitting
Therefore, considering the induction-time (t0 ) offsetting the paramet- of these portions gives straight lines and plotting them (j vs. t) by
ric form of the classic SM model,19 associated with the Fe 3D nu-
cleation and diffusion-controlled growth mechanism, can be rewritten
as: 0.0012
j3D (t) = P1 (t − t0 )−1/2

  0.0010
-1.06
1 − exp(−P3 (t − t0 ))
1 − exp −P2 (t − t0 ) − [6] -1.04
P3
0.0008
-2

where: -1.02
j / Acm

z F D 1/2 c0
P1 = [6a] 0.0006 -1.00
π1/2
-0.98 -0.96
0.0004
P2 = N0 πD(8πMc0 /ρ) 1/2
[6b] -0.94

0.0002 -0.92

P3 = A [6c]
0.0000
where ρ is the density of the Fe deposit and M is its atomic mass, N0 0 5 10 15 20 25 30
is the number density of active sites on the electrode surface, and A is t/s
the nucleation frequency per active site.
Figure 4 depicts the comparison between the experimetal j-t plots Figure 4. Comparison between the experimental current density transients
and the theoretical curves obtained from fitting Eq. 6 to the experi- ( ) recorded during the iron electrodeposition onto the GCE and the theoretical
mental data. The theoretical model using Eq. 5 fits well the behavior ones (solid lines) after fitting Eq. 6 to the experimental data after induction-time
of the experimental data recorded onto the GCE. Kinetic parameters correction.

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 Journal of The Electrochemical Society, 165 (16) D808-D812 (2018) D811

Table I. Best-fit parameters and kinetic data obtained from the experimental current-time transient in Figure 2 using Eq. 6.

-E/V 103 P1 /A s1/2 cm−2 P2 /s−1 A/ s−1 10−6 N0 / cm−2 107 D/ cm2 s−1 10−6 AN0 / s−1 cm−2 t0 / s
0.92 1.70 ± 0.03 0.108 ± 0.001 0.281 ± 0.004 3.48 ± 0.03 1.00 ± 0.03 0.98 ± 0.02 5.23 ± 0.03
0.94 1.80 ± 0.03 0.126 ± 0.001 0.271 ± 0.003 3.75 ± 0.03 1.08 ± 0.04 1.02 ± 0.01 4.32 ± 0.03
0.96 1.70 ± 0.03 0.189 ± 0.003 0.317 ± 0.003 5.97 ± 0.10 1.02 ± 0.04 1.89 ± 0.04 3.41 ± 0.03
0.98 1.70 ± 0.03 0.405 ± 0.005 0.175 ± 0.002 12.80 ± 0.17 1.02 ± 0.04 2.23 ± 0.04 3.05 ± 0.03
1.00 1.80 ± 0.03 0.226 ± 0.002 1.425 ± 0.058 6.46 ± 0.10 1.13 ± 0.04 9.20 ± 0.40 2.21 ± 0.03
1.02 1.80 ± 0.03 0.400 ± 0.002 1.546 ± 0.040 11.53 ± 0.10 1.12 ± 0.04 17.80 ± 0.49 2.03 ± 0.02
1.04 1.80 ± 0.03 0.821 ± 0.002 0.842 ± 0.014 23.18 ± 0.10 1.14 ± 0.04 19.50 ± 0.34 1.81 ± 0.02
1.06 1.90 ± 0.03 1.161 ± 0.062 0.712 ± 0.010 30.19 ± 1.62 1.23 ± 0.04 21.50 ± 1.19 1.52 ± 0.02

extrapolation, one can obtain the induction-time, t0 , as they intercept
the time axis at t = t0 (see Figure 5). From this exact evaluation of
t0 , the values thus obtained were introduced in Eq. 6 to corroborate
the previous results from the first approach. The t0 values taken from
Figure 5 give practically the same kinetic parameter results (with a
standard deviation of approximately ± 0.12 s) as shown in Table I,
which indicates that both methods are valid.
Surface characterization (SEM, EDS, and XPS).—Figure 6
shows the SEM images at different magnifications using a poten-
tiostatic regime from the DES at 70◦ C, while Figure 7 depicts the
EDS analysis of the surface deposit at sites of interest: large growth
clusters (Zone 1) and the nanoparticles (Zone 2). Both spectra ob-
tained on these zones confirm the presence of Fe on the deposit. The
oxygen peak observed in Figure 7 could be associated with the Fe
oxidation during the process.
In Figure 6d, one can observe that Fe clusters exhibit a cauliflower-
like morphology with a relatively homogenous distribution (see
Figure 6a). It is worth noting that these colonies in Zone 1 are
constituted by Fe nanoparticles (see Figure 6d), similar to Zone 2.
Furthermore, Figure 6 clearly indicates the nucleation of Fe clusters
on the GCE surface follows the electrochemical aggregative growth
mechanism (aggregation + self-alignment) described by Ustarroz
et al.26–29
Additionally, the XPS spectra analysis displayed in Figure 8 con-
firms the presence of the Fe metallic phase (previously seen from
Figure 7) formed in the deposit. The fitting of the XPS profiles helps
determining that the deposit is constituted by Fe(0) (35.7%) and a mix-
ture of FeO (36.5%), Fe2 O3 (16.8%) oxides, and hydroxide, Fe(OH)3
(11%), which could be formed by the easy oxidation of the Fe surface
deposit in contact with the air after the sample preparation and during
its transfer to the analysis as expected.
Conclusions
The iron electrodeposition and nucleation and diffusion-controlled
growth mechanisms were studied and explained, for the first time,
from a choline chloride-based eutectic mixture. The model based on
a 3D nucleation and diffusion-controlled contribution with the induc-
tion time correction was proposed and validated to explain the iron
nucleation and diffusion-controlled growth onto glassy carbon elec-
trode and to obtain kinetic parameters of interest. The iron electrode-
position from the DES occurred through the progressive nucleation
mechanism, which was also verified by SEM micrographs showing
the formation of iron nanoclusters (nuclei) with different ages on
the electrode surface. The induction time plays an important role in
the formation of these Fe clusters and leads to an electrochemical
aggregative growth mechanism. It was found that the deposits were
constituted by particles of Fe(0) and a mixture of FeO, Fe2 O3 and
Fe(OH)3 .
Acknowledgment
T.L.M. thanks SEP-PRODEP for the postdoctoral scholarship
granted. The authors like to thank CONACyT for projects 237327
and 258487 and SEP-PRODEP for RedNIQAE. The authors also
thank the SNI for the distinction of their membership and Ing. Adolfo

0.0006
-1.06 -1.04
-1.02
-1.00

-0.98

0.0004
2
j / Acm

-0.96

-0.94

0.0002 -0.92

0.0000
1 2 3 4 5 6 7 8 9 10 11 12

t/s

Figure 5. Induction time determination through the plots of rising parts of the Figure 6. SEM images corresponding to the surface of GCE electrodeposited
experimental current density transients ( ) and the linear fitted ones (line) at with iron at – 1.04 V during 70 s at different magnifications: a) 5,000, b)
the potentials indicated in V. 10,000, c) 20,000 and d) 120,000 X.

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 D812 Journal of The Electrochemical Society, 165 (16) D808-D812 (2018)

Figure 7. EDS analyses of the iron surface deposit onto the GC, a) Zone 1, b) EDS spectrum of Zone 1, c) Zone 2, and d) EDS spectrum of Zone 2.

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