Journal of The Electrochemical Society, 166 (15) H783-H790 (2019) H783

0013-4651/2019/166(15)/H783/8/$38.00 © The Electrochemical Society

A Facile Route to Synthesize a TiNT-RuO2 Electrocatalyst for

Electro-Generated Active Chlorine Production
D. Elizarragaz,1,= J. E. Carrera-Crespo,2,= J. Vazquez-Arenas, 3,z
I. Romero-Ibarra,4
E. J. Ruiz-Ruiz, 1,z and I. Chairez2
1 Universidad Autónoma de Nuevo León, UANL, Facultad de Ciencias Químicas, Cd. Universitaria, San Nicolás de los
Garza, Nuevo León, C.P. 66455, México
2 Unidad Profesional Interdisciplinaria de Biotecnología, Instituto Politécnico Nacional, La Laguna Ticomán,
07340 Ciudad de México, México
3 Centro Mexicano para la Producción más Limpia, Instituto Politécnico Nacional, Col. La Laguna Ticomán,
07340 Ciudad de México, México
4 Unidad Profesional Interdisciplinaria en Ingeniería y Tecnologías Avanzadas-Instituto Politécnico Nacional. Gustavo
A. Madero, C.P. 07340 Ciudad de México, México

This study aimed to fabricate a novel TiNT-RuO2 electrocatalyst to produce active chlorine with the capacity to oxidize recalcitrant
organic matter. Titanium oxide nanotubes (TiNTs) were first grown via Ti foil anodization in potentiostatic mode in an ethylene glycol
solution containing H2 O and NH4 F and then annealed at 450°C in air. RuO2 nanoparticles were deposited on the TiNTs using a hybrid
strategy that included pulsed electrodeposition of the Ru nanoparticles, followed by thermal treatment. X-ray diffraction (XRD) only
revealed peaks related to metallic Ti and anatase (TiO2 ) for the TiNTs, whereas additional peaks associated with the tetragonal
RuO2 structure were shown for TiNT-RuO2 . Scanning electron microscopy showed a well-organized structure for the TiNTs with an
average inner diameter of approximately 185 nm for the NTs, while RuO2 nanoparticles (size <10 nm) were homogenously deposited
on the walls and around the openings of the TiNTs. TiNT-RuO2 preferred the active chlorine formation over oxygen evolution owing
to the presence of the RuO2 nanoparticles. Rapid degradation testing revealed complete elimination of picloram (PCL) in 2 h when
10 mA cm−2 was imposed on the TiNT-RuO2 , whereas 48% of the 2,4-dichlorophenoxyacetic acid (2,4-D) was removed under the
same conditions using the electro-generated active chlorine on the TiNTs.
© 2019 The Electrochemical Society. [DOI: 10.1149/2.0071915jes]

Manuscript submitted June 7, 2019; revised manuscript received September 29, 2019. Published October 25, 2019.

The formation of electro-generated active chlorine on anodes has
gained renewed interest as an indirect oxidant of recalcitrant organic
compounds (e.g., dyes, pesticides, and pharmaceutical compounds)
in chloride media.1–4 The chlorine mechanism (CM) typically relies
on the strength of three oxidizing species (Cl2 /Cl − E°° = 1.36 V vs.
SHE, HClO/Cl − E° = 1.49 V vs. SHE, and ClO− /Cl − E ° = 0.89 V
vs. SHE), predominating at different pH values. Importantly, the oxi-
dizing power of electro-generated chlorine species (i.e., adsorbed on
the anode surface) contrasts against typical aqueous chlorine species,
which are very stable in solution. Confirming this idea, the destruc-
tion of crystal violet was considerably higher when active chlorine was
electro-generated on an electrode surface than when directly incorpo-
rated as sodium hypochlorite into the solution at similar concentration
conditions.5 This drew attention since similar activities could be ex-
pected for these chlorine species, presenting analogous structures and
thus suggesting an essential distinction between soluble and electro-
generated (adsorbed) active chlorine species. In this direction, De Bat-
tisti group6 theoretically proposed a variation of the mechanism for
electrochemical incineration of organics proposed by Comninellis,7
which is applicable to active chlorine in which chloro and oxychloro
radicals “co-adsorbed” (HOClads ) on the anode surface play impor-
tant roles in the pollutant mineralization, rather than soluble chlorine
species, along with the co-electrosorption of hydroxyl radicals.
The discovery of RuO2 -based dimensionally stable anodes (DSAs)
for chlor-alkali cells triggered research on low cost and durable mate-
rials, emphasizing the role of the anode phase for this electrocatalytic
application.8,9 DSAs are typically constituted by a thin film made of a
conductive oxide (i.e., RuO2 ) deposited on Ti, and their shape does not
change when subjected to severe anodic attacks during electrolysis.9
This technology has somehow consolidated over the years; thus, the
exploration of new DSAs started to focus on investigating electrocat-
alytic aspects concerning the active chlorine generation for pollutant
destruction. Although this mechanism could involve any of the three
aforementioned oxidants depending on the pH, attention has been par-
ticularly paid to the formation of HClOads species in the pH range of
=
These authors contributed equally to this work.
z
E-mail: jorge_gva@hotmail.com; edgar.ruizrz@uanl.edu.mx
2 to 7.10 Additionally, this oxidant is generated in a large amount and
with adequate oxidation potential for environmental applications, as
described in a recent study.11 Of note, in this pH range, Cl2 has not
been detected on the electrode surface by differential electrochemical
mass spectroscopy (DEMS).
In general, the electroactive phase of DSA is typically deposited
on a Ti substrate, which has been preferred over other surfaces owing
to its excellent mechanical, thermal, and stability features,12,13 which
have been derived from multiple nano- and micro-structures with a
rich diversity of textural and electronic properties.14,15 Specifically,
titanium oxide nanotubes (TiNTs) have stood out for electrocatalytic
applications owing to their large specific surface area, semi-conductive
features, adsorption capacity, adherence, and dispersion of different
active phases, among other reasons.14,16 Accordingly, they have be-
come a typical substrate for the design and development of elec-
trocatalysts, including Au,17 Pt,18,19 Pd,20,21 Sb-doped SnO2 ,22,23 Ni
nanoparticles,24 Ni nanoparticles with Cu,25 and β-PbO2 /α-PbO2 /Sb–
SnO2 .26 However, RuO2 coatings on TiNTs have been barely evaluated
for the destruction of organic-persistent compounds via the electro-
catalytic CM. A recent study carried out thermal decomposition to
deposit RuO2 on anodized TiNTs, and the electrode was only tested
for electrochemical chlorine generation.27 Nevertheless, this synthesis
method favors the formation of a RuO2 coating to obstruct the mouth of
the TiO2 NTs, as confirmed by scanning electron microscopy (SEM)
images. A more suitable method to considerably increase the number
of electroactive sites formed by RuO2 would be the electrocrystalliza-
tion of nanoparticles, which could benefit from the large specific sur-
face area of TiNTs and the adhesion and compatibility between these
two phases because TiO2 and RuO2 crystals share similar tetragonal
structures and have close lattice parameters.28 This method could also
be more controllable, and this electrocatalyst could be quickly fabri-
cated on an industrial scale by using a DC power supply. In addition,
the oxidation ability of chlorine species produced from TiNT-RuO2
needs to be assessed against recalcitrant compounds, which has not
been conducted thus far. Therefore, we fabricated for the first time
a TiNT-RuO2 electrocatalyst using only electrochemical methods to
yield active chlorine species with the capacity to oxidize recalcitrant
organic matter. To avoid clogging formation over the mouth of the
TiO2 NTs, the RuO2 nanoparticles were synthesized using a hybrid

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 H784 Journal of The Electrochemical Society, 166 (15) H783-H790 (2019)
strategy consisting of Ru nanoparticle nucleation on a TiO2 support
via pulse potential techniques, followed by thermal treatment to ob-
tain the RuO2 nanoparticles. The idea is to provide a rapid alternative
to the typical chemical synthesis of these catalysts using a sol-gel or
polymeric precursor (Pechini), which generally requires days to fab-
ricate a single electrode. Additionally, RuO2 is efficiently deposited
using a very low load of this metal, which reduces costs compared
to that of traditional synthesis methods (e.g., sol-gel, hydrothermal,
and Pechini). TiNTs were used as the substrate rather than a typi-
cal flat TiO2 surface during electrocatalysis to enable Ru deposition
and provide mechanical integrity to the dimensionally stable anode.
Although Ti oxides are typically not electrocatalytic for most electro-
chemical reactions, they can alter the dielectric properties of the films
deposited on them.29 Then, the electrocatalyst was micro-structurally
characterized by XRD and texturally characterized using SEM. An
electrochemical characterization was conducted in 0.05 M NaCl to
evaluate the eventual production of active chlorine and to perform
rapid testing concerning the degradation of a commercial formulation
of Tordon 101 comprised of a mixture of the herbicides 2,4-D (39.2%
w/v) and PCL (10.2% w/v) (molecule test), and excipients (50.2% w/v,
reported as water, ethanol, and surfactants). The concentration decay
of the initial molecules and the intermediate formation arising from
the degradation process were tracked using high-performance liquid
chromatography (HPLC).
Materials and Methods
Chemicals.—PCL and 2,4-D analytical standards were supplied by
Sigma Aldrich, while the commercial formulation of these herbicides
(Tordon 101) was supplied by Dow AgroSciences. Ruthenium chlo-
ride (RuCl3 ), ammonium fluoride (NH4 F), ethylene glycol, ethanol,
sodium chloride (NaCl), potassium perchlorate (KClO4 ), sodium sul-
fate (Na2 SO4 ), potassium iodide (KI), and ammonium heptamolybdate
were analytical grade reagents and used as received. All solutions were
prepared with ultrapure water (Milli-Q Direct 8 system, Millipore,
18 M·cm). A titanium foil (Alfa Aesar, 0.25-mm thickness, 99.5%
purity) was used to fabricate the electrodes.
Preparation of electrodes.—TiNTs and TiNT-RuO2 were fabri-
cated with an exposed area of 3.0 cm2 using potentiostatic anodization
of Ti foils at 70 V for 50 min in a two-electrode cell by employing
a Pt wire (Alfa Aesar, 99.99%) as the counter electrode in an ethy-
lene glycol solution containing H2 O (15 wt%) and NH4 F (0.3 M). The
TiNTs formed were washed with ultrapure water and ethanol and dried
for 30 min at room temperature; then, they were annealed at 450°C
for 30 min in air using a ramp temperature of 5°C min−1 . To de-
posit RuO2 nanoparticles on the TiNTs using a hybrid strategy, TiNTs
were immersed in a 70:30 (% v/v) H2 O:ethanol KClO4 saturated so-
lution that contained 0.005 M RuCl3 . The pulsed electrodeposition of
the Ru nanoparticles on the TiNTs was conducted in a conventional
three-electrode cell with TiNTs as the working electrode and a glassy
carbon plate and Ag/AgCl electrode, as the counter and reference elec-
trodes, respectively, using the following conditions: Eon = −3 V vs.
Ag/AgCl, ton = 0.3 s, Eoff = OCPinitial , toff = 1 s for 300 cycles. Subse-
quently, the TiNTs-Ru were washed with ultrapure water and dried at
room temperature for 30 min and then annealed in an air atmosphere
at 450°C for 30 min using a ramp temperature of 5°C min−1 to fi-
nally obtain the TiNT-RuO2 electrocatalyst. The total time required
for the electrocatalyst synthesis was approximately 18 h. Of note, the
above procedure guarantees the homogeneity and good dispersion of
the RuO2 phase, unlike depositing Ru on amorphous TiNTs (with-
out calcination) and then applying the thermal treatment to both. This
pathway would generate a heterogeneous deposition of Ru owing to
the absence of crystallinity (i.e., poor electronic conductivity) in the
NTs.
Structural and electrochemical characterization of anodes.—
SEM images were obtained for the TiNT and TiNT-RuO2 anodes with
a high-field emission microscope (JMS-7600F) using an accelerating
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voltage of 5.0 kV and equipped with energy dispersive X-ray spec-
troscopy (EDS) capabilities for elemental analysis. The crystal struc-
ture of the electrodes was determined using an X-ray diffractometer
(Bruker D-8 Advance with Cu-Kα radiation) in the grazing incidence
X-Ray diffraction (GIXRD) geometry by fixing the incident beam an-
gle at 5.0°. X-ray data was analyzed using HighScore Plus software
V.3.0.5 (PANalytical B.V., Almelo, Netherlands). The electrochemical
characterization was carried out in a VMP3 (Bio-Logic Science In-
strument) potentiostat/galvanostat controlled by EC-Lab software that
was equipped with a frequency response analyzer (FRA) by employ-
ing a three-electrode cell (200 mL) and using TiNTs or TiNT-RuO2 as
the working electrode and a graphite rod (30.0-cm length × 1.016-cm
diameter, Alfa Aesar, 99.997%) and Ag/AgCl (0.197 V vs. SHE) as
the counter and reference electrodes, respectively. Cyclic voltamme-
try (CV) was conducted in 0.05 M NaCl at 20 mV s−1 to evaluate
the electrochemical activity of the electrocatalysts toward the chlo-
rine evolution reaction (CER) mechanism. The O2 (air) dissolved in
the electrolyte was not removed. Electrochemical impedance spec-
troscopy (EIS) characterization of the electrodes was performed in a
0.05-M Na2 SO4 solution at 1.2 V vs. Ag/AgCl with an AC perturbation
of ± 10 mV in the frequency range of 100 kHz to 0.1 Hz.
The concentration of active chlorine species was tracked by iodo-
metric methods according to Refs. 1,2,11. Aliquots sampled from the
electrochemical cell were added to a quartz cell containing potassium
iodide (0.1 M) and ammonium heptamolybdate (0.01 M). The ab-
sorbance was recorded after 2 min of reaction at 350 nm using a Cary
5000 UV-Vis-NIR spectrophotometer.
Electrochemical degradation via active chlorine.—The produc-
tion of active chlorine on the TiNT-RuO2 electrode was tested for the
degradation of Tordon 101, which is a commercial formulation con-
taining the herbicides 2,4-D (39.2% w/v) and PCL (10.2% w/v) and
excipients reported as isopropanol (5.0% w/v), alkylphenol alkoxylate
(5.2% w/v), triisopropanolamine (1.3% w/v), and other related com-
pounds (39.1% w/v).30 The degradation was carried out via in situ
electrochemical generation of the active chlorine species in a reactor
containing 150 mL of 0.05 M NaCl (pH 5.8) and an initial concen-
tration of Tordon 101 that was equivalent to 30 and 144 mg L–1 of
PCL and 2,4-D, respectively. The imposed current density was tested
at 10 mA cm–2 for 120 min, and sampling was conducted every 20 min
to analyze the concentration decay of the pesticides and evolution of
subproducts (i.e., formic and oxalic acids). To evaluate the degradation
performance of electro-generated active chlorine (i.e., that formed on
the electrocatalyst), a control degradation test was conducted using
1 M hypochlorous acid (i.e., soluble chlorine) for Tordon 101 under
the same conditions as established above (reactor volume of 150 mL,
initial concentrations of 30 and 144 mg L–1 for PCL and 2,4-D, re-
spectively). The pH of the initial solution was adjusted to 5.8 with
HCl.
The decay of PCL and 2,4-D concentrations was monitored by
HPLC using a Hyperclone C-18 reversed phase as the stationary phase
(250 mm × 4.6 mm, 5-μm particle size, from Phenomenex), a mixture
of acidified H2 O with H3 PO4 at pH 2.4, and acetonitrile (60:40 V/V) in
isocratic elution mode as the mobile phase at 0.8 mL min−1 . The PCL
and 2,4-D compounds presented maximum absorbance at 224 nm;
therefore, this wavelength was used to detect these compounds at dif-
ferent retention times. The injection volume and temperature of the
column were 20 μL and 25°C, respectively.
The evolution of organic acids was monitored by HPLC using
a Prevail organic acids column (150 mm × 4.6 mm, 5-μm particle
size, from Alltech-Grace), and phosphate buffer (0.25 M at pH 2.5) as
the mobile phase in isocratic elution mode at 0.8 mL min–1 . Formic
(Carbon oxidation state, +II) and oxalic (Carbon oxidation state, +III)
acids were detected at 200 nm. The formation of these intermediates
during the degradation of PCL and 2,4-D indicated that the oxidation
of these contaminants was close to full mineralization (CO2 and H2 O).
The injection volume and temperature of the column were 30 μL and
25°C, respectively.
 Journal of The Electrochemical Society, 166 (15) H783-H790 (2019)
a) TiNTs b) TiNTs-RuO2
c) TiNTs d) TiNTs-RuO2
Figure 1. SEM images of synthesized TiNTs and TiNTs-RuO2 collected at
different magnifications: a, b) 50.0 and c, d) 500.0 K.
Results and Discussion
Electrode characterization.—Figure 1 shows the surface of the
as-synthesized TiNT (a, c) and RuO2 -TiNT (b, d) anodes at different
SEM magnifications. In particular, Figs. 1a and 1c show the well-
organized structure of the TiNTs with inner diameters ranging from
180 to 190 nm. Figures 1b and 1d reveal the nanoparticles of RuO2
(sizes of <10 nm) deposited on the walls and around the mouths of the
TiNTs without blocking them, unlike a recent study.27 It is of primary
concern to achieve this distribution during plating to guarantee the
mechanical and structural integrity of the nanotubes during use and to
increase the electroactive area of the catalyst by decreasing the particle
size, assuming some RuO2 nanoparticles are deposited in the inner and
outer walls of the TiNTs. Figure 2 shows the EDS analysis conducted
of the TiNT-RuO2 , which resulted in the following average elemental
composition of the surface: oxygen (O K 40.2 wt%), titanium (Ti
K 54.6 wt%), and ruthenium (Ru L 3.1 wt%). Fluor (F K 1.4 wt%)
was also found as a synthesis residue because the TiNTs were grown
using an electrolyte containing NH4 F. This compositional analysis
confirmed the elements contained in the catalyst, and in particular, the
good dispersion and very low load of Ru, as displayed by its elemental
mapping and low-intensity peaks in the EDS spectrum, respectively
(Fig. 2).
The grazing incidence X-ray diffraction (GIXRD) patterns of the
TiNTs and TiNT-RuO2 are displayed in Fig. 3. As observed for bare
TiNTs, only peaks associated with metallic titanium and the anatase
phase of TiO2 (pdf 00-021-1272) were detected. No peaks related
to rutile (TiO2 ) were found because the calcination temperature was
450°C, where the anatase phase (TiO2 ) preferentially predominates. In
Figure 2. a) EDS analysis and b) mapping for Ru element in the synthetized TiNTs-RuO2 .
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H785
general, the anatase phase was favored when the calcination temper-
ature in the air atmosphere was below 600°C.31,32 These signals were
also detected in the GIXRD pattern obtained for TiNT-RuO2 with
similar intensities, revealing the non-agglomerated coating of the ac-
tive phase. Thus, the peaks associated with the anatase phase dimin-
ished when the GIXRD geometry was used owing to the presence
of large agglomerates of the deposited phases (i.e., CdS) on top of
TiO2 nanotubes.33 Likewise, the crystal structure of TiO2 (pdf 00-
021-1272) in the TiNT-RuO2 was predominantly the anatase phase as
previously discussed, indicating that RuO2 loading does not change
the crystal structure of the TiNTs.34 Thus, three small peaks at 2θ =
28.0°, 35°, and 54° were measured, corresponding to (110), (011),
and (211) diffraction planes of RuO2 , respectively (tetragonal struc-
ture) (pdf 00-040-1290).35 The samples were analyzed using GIXRD
owing to the low amount of RuO2 , which hampered its detection in
the diffractograms obtained via Bragg–Brentano arrangement, where
only the peaks associated with metallic Ti and TiO2 were observed.
No other peaks related to an additional phase were observed in this
study, confirming the synthesis of the TiNT-RuO2 electrocatalyst via
the facile route to decorate RuO2 nanoparticles on the TiNTs. Note that
the crystalline structure (i.e., tetragonal) of RuO2 similarly adopted the
structure of the TiO2 anatase phase (pdf 00-021-1272) that was used
as the substrate. This showed the clear effect of the substrate on the
catalysis of the electroactive phase.
Electrochemical characterization.—The voltammetry characteri-
zation was initially performed with the TiNTs and TiNT-RuO2 electro-
catalysts to analyze the oxidation processes occurring on the surfaces.
Figure 4a shows the voltammograms measured from the initial OCP
(0.026 V vs. Ag/AgCl) to the positive direction for bare TiNTs in
0.05 M NaCl and in 0.05 M Na2 SO4 solutions under stagnant condi-
tions, where it was clear that significant faradaic contributions (i.e.,
charge transfer) were not observed in any of these electrolytes within
the evaluated potential window. In fact, when the potential scan was in-
verted in the negative direction, no peaks associated with the reduction
of recently oxidized species were detected in the curves. Most likely,
this behavior was due to the semi-conductive features of TiNTs be-
cause they generally are poor electronic conductors. However, TiNTs
play an important role as substrates that modify the dielectric prop-
erties of the top film (i.e., RuO2 ), as revealed by an in-depth analysis
of the composition gradients in Ti/SnO2 -Sb2 O5 anodes composed of
multiple layers of Sn and TiO2 .29 Additionally, this substrate confers
mechanical and electrical stabilities for producing a dimensionally
stable anode. However, when the potential sweep was initiated in the
positive direction over TiNT-RuO2 in sulfate media, an increase in
current density was observed at approximately 0.8 V (vs. Ag/AgCl),
which has been associated with H2 O oxidation to form O2 , because
there are no other species to overcome oxidation in this potential range.
Under this condition, it is not expected that the RuO2 phase will mod-
ify the electronic conductivity of the TiNTs; rather, it acts as an active
 H786 Journal of The Electrochemical Society, 166 (15) H783-H790 (2019)
Figure 3. Grazing incidence X-Ray diffraction patterns of synthesized TiNTs and TiNTs-RuO2 , obtained by fixing the incident beam angle at 5.0°.
site for electrochemical reactions. The occurrence of the oxygen evo-
lution reaction (OER) on the RuO2 phases in sulfate electrolytes have
been previously reported in the literature.1–3,11,13 When the potential
is reversed toward the cathodic direction, reduction waves are not de-
tected because the TiNT-RuO2 phase is not catalytic to reduce O2
(i.e., dissolved into the electrolyte from air). When this material is
exposed to 0.05 M NaCl, the onset voltage of the oxidation process
is displaced to more positive values (∼1 V) compared to that of the
OER in sulfate media (refer to Fig. 4a). A comparison with a Ti/RuO2
anode synthesized via the polymeric precursor (Pechini) method re-
vealed that the onset potential for chloride oxidation was positively
displaced by approximately 100 mV more positive (∼1.1 V, Fig. 4b in
Ref. 2). However, the current density significantly surpassed the one
for our electrode material owing to the considerably larger loading of
RuO2 , as observed by the very intense peaks for this metal oxide in the
diffractogram of the Ti/RuO2 Pechini sample obtained via the Bragg–
Brentano configuration.2 The occurrence of the anodic processes de-
scribed in Fig. 4a suggests that the main reaction mechanism occurring
on the electrode surface was modified; in fact, the slope of the voltam-
mogram was steeper than the one obtained for Na2 SO4 . Under this
premise, active chlorine formation presumably occurs once the cur-
rent flows on the catalyst/electrolyte interface, which was confirmed
when the potential was inverted in the negative direction (Fig. 4a),
where a peak related to the reduction of the active chlorine species
was recorded. According to the bulk pH of the electrolyte (5.8), this
peak could be attributed to reduction of HClOads , according to recent
studies of the CER mechanism carried out with DEMS11 and the frac-
tion diagram presented in Fig. 8. The OER began at some point during
the oxidation scan as a parasitic reaction. The reaction mechanism for
the occurrence of this chlorine species will be discussed in Degrada-
tion of PCL and 2,4-D and evolution of its byproducts section.
To confirm the occurrence of the cathodic peak in Fig. 4a, cyclic
voltammograms were recorded in chloride media at different anodic
inversion potentials of 1.2, 1.6, and 1.7 V (vs. Ag/AgCl) under stag-
nant conditions (Fig. 4b). As observed, the cathodic wave was only
detected in the last two inversion potentials, and it grew considerably
by increasing this value from 1.6 to 1.7 V (vs. Ag/AgCl), indicat-
ing a higher generation of chlorine species on the electrode surface.
Probably, this cathodic wave was not observed at the least positive
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inversion potential owing to the facile desorption of chlorine species
from the TiNT-RuO2 surface. Accordingly, a voltammogram was
recorded under the same experimental conditions but with constant
stirring. Surprisingly, the cathodic wave disappeared when the volt-
age was inverted at 1.7 V (Fig. 4b - stirred) owing to the convection
applied to the electrode, confirming the facile desorption of the elec-
trogenerated active chlorine species from the electrocatalyst. Note that
some of these adsorbed species can be in gaseous form, whereby their
separation from the electrode surface can readily occur. Additionally,
the TiNT-RuO2 electrode remained stable after undergoing different
CV cycles (not shown), which demonstrated its stability and main
denomination as a “dimensionally stable anode”.
To understand the effect of RuO2 on the electrical properties of
TiNTs, EIS measurements were performed in 0.05 M Na2 SO4 under
the potentiostatic mode at 1.2 V (vs. Ag/AgCl) for both TiNT-based
electrodes and at 0.6 V (vs. Ag/AgCl) only for the TiNT-RuO2 elec-
trode. The first potential was selected because it enables the charac-
terization of the H2 O oxidation without the production of a significant
amount of bubbles from O2 evolution. Figure 4c shows the Nyquist
plots recorded for bare TiNTs and TiNT-RuO2 electrodes at 1.2 V
(vs. Ag/AgCl), where the arc radius of the TiNTs abruptly decreased
when the nanotubes were decorated with RuO2 nanoparticles; this in-
dicated that this phase significantly improved the charge transfer to
perform the OER, as previously shown in Fig. 4a. The experimental
EIS spectra were fitted using the ZView software using the equiv-
alent electric circuit (eec) shown in the inset of Fig. 4c. This eec
has been previously reported for the analysis of electrodes based on
TiO2 nanostructures,33,36–38 where Rs is the solution resistance, Rf is
the charge transport resistance in the internal film (TiNTs or TiNT-
RuO2 ), and Rct is the charge transfer resistance between the electrode
surface and the electrolyte. Qsc and Qdl are constant phase elements
(CPE) associated with the space charge capacitance and the double
layer capacitance, respectively. As observed in Table I, when TiNTs
were coupled with RuO2 nanoparticles, the Rct decreased four orders
of magnitude compared to the values obtained for the bare TiNTs,
confirming that the RuO2 noticeably improved the electrocatalyst per-
formance of the NTs. Moreover, the Rf and Rct significantly decreased
when the potential was changed from 0.6 V to 1.2 V (vs. Ag/AgCl)
for the TiNT-RuO2 electrode, showing that a more positive potential
 Journal of The Electrochemical Society, 166 (15) H783-H790 (2019)
Table I. Parameters obtained by fitting of the experimental EIS spectra using the equivalent electric circuit shown in the inset of Fig. 4c.
Electrode E (V vs. Ag/AgCl) Rs (Ω cm2 )
TiNTs 1.2 48.9
TiNTs-RuO2 0.6 46.6
1.2 53.7
reduces the energy barriers of this electrode for electronic conduction
and charge transfer to perform chloride oxidation and the OER.
Estimation of the active chlorine production by chemical analy-
sis is crucial to confirm its occurrence during chloride oxidation over
TiNT-RuO2 , as shown in Fig. 4. Therefore, iodometric titration was
performed during electrolysis conducted in 0.05 M NaCl and 0.05 M
Na2 SO4 over TiNT-RuO2 by applying a constant current density of
Figure 4. Cyclic Voltammetric characterization conducted at 20 mV s−1 for:
a) bare TiNTs and TiNTs-RuO2 in the electrolytes indicated in the figure, and
b) TiNTs-RuO2 in an electrolyte containing 0.05 M NaCl at different inversion
potentials (Einv ). c) Nyquist plots obtained in 0.05 M Na2 SO4 at 1.2 V vs.
Ag/AgCl for bare TiNTs and TiNTs-RuO2 . Inset: zoom of Nyquist spectra
displaying fitted curves calculated using the equivalent electric circuit shown
in this figure.
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H787
Rf (Ω cm2 ) Qdl (F sn cm−2 ) n Rct (Ω cm2 )
6940.8 0.4 × 10−5 0.9 4.5 × 106
1.3 × 109 2.1 × 10−5 0.9 4.4 × 106
16.4 2.7 × 10−5 0.9 717.5
10 mA cm–2 to track the formation of oxidants in these media. Fig-
ure 5 shows the evolution of the oxidants over 240 min, where it is
evident that its concentration (absorbance) increased up to 180 min,
achieving a quasi-steady behavior after that time. This oxidant de-
tected in the curve was mainly associated with HClO desorbed from
the electrocatalyst surface (i.e., HClOads ) according to the discussion
above regarding the voltammetry study. This was because oxidants
were not observed when a similar iodometric test was conducted in
Na2 SO4 , where O2 was the main oxidant (Fig. 5).
Degradation of PCL and 2,4-D and evolution of its byproducts.—
We conducted rapid testing of the electrode capacity to form active
chlorine, and its potential utilization as an oxidant for the degrada-
tion of recalcitrant compounds (i.e., pesticides) was examined. Thus,
a more detailed analysis (i.e., HPLC-MS) of the chemical composi-
tion associated with the intermediate products resulting from the PCL
and 2,4-D elimination will be the motivation of a forthcoming study.
Figure 6a shows the relative percentage decay of PCL ([PCL]initial :
30 mg L–1 ) and 2,4-D ([2,4-D]initial : 144 mg L–1 ) as a function of the
electrocatalysis time using TiNT-RuO2 as the anode and applying dif-
ferent current densities (5 and 10 mA cm–2 ). Therefore, the decrease
in the pesticide concentration as a function of the electrolysis time (t)
results from the in situ electrogeneration of active chlorine species.
These curves are displayed with their relative values (with respect to
the initial concentration), i.e., [PCL]rel = [PCL]t / [PCL]initial , [2,4-D]rel
= [2,4-D]t / [2,4-D]initial . As observed in Fig. 6a, complete degradation
of PCL was achieved in 2 h of electrocatalysis when 10 mA cm–2 was
applied on the electrode, while 90% of degradation was reached in
the same time when 5 mA cm–2 was used. However, the concentration
decays of 2,4-D were 42 and 48% when 5 and 10 mA cm–2 were ap-
plied, respectively. Under this condition, the initial degradation rates
of PCL and 2,4-D seemed to slightly depend on the current density,
although higher degradation values were somewhat observed when
j increased. These rate differences can be more clearly observed in
Fig. 6b, assuming that the degradation of PCL and 2,4-D follows a
pseudo-first order kinetics, suggesting typical mass transfer control
that is presumably associated with the transport of contaminants to
become in contact with the oxidants. The apparent constant (k) and
coefficient of determination (R2 ) for PCL were 1.8 × 10–2 min–1 (R2
= 0.9934) and 2.6 × 10–2 min–1 (R2 = 0.9795) at 5 and 10 mA cm–2 ,
Figure 5. Evolution of active chlorine species conducted in 0.05 M NaCl (blue
circles) and 0.05 M Na2 SO4 (red squares) on TiNTs-RuO2 at 10 mA cm−2 (pH
5.8 and 25°C), and measured by iodometric titration methods.
 H788 Journal of The Electrochemical Society, 166 (15) H783-H790 (2019)

Figure 6. a) Relative decay of 2,4-D and PCL concentrations (C0 = 144 and 30 mg L−1 , respectively) during destruction with electrogenerated active chlorine
in 0.05 M NaCl (pH 5.8 and 25°C) on TiNTs-RuO2 at 5 (red line) 10 mA cm−2 (blue line); and b) pseudo-first order degradation kinetics of contaminants: PCL
(squares) and 2,4-D (triangles).

respectively; and for 2,4-D, they were 3.0 × 10–3 min–1 (R2 = 0.9310) acids as the main subproducts of PCL destruction using commercial
and 4.8 × 10–3 min–1 (R2 = 0.9927) at 5 and 10 mA cm–2 , respec- DSA (Ti/Ru0.3 Ti0.7 O2 ), where the maximum concentrations were de-
tively. From these results, the increase in the degradation rate could tected for both acids in 60 min of reaction, and their almost complete
result from the yield of the electro-generated active chlorine species, degradation was reached after 120 min of electrocatalysis. Contrary
which was mostly HOCl, according to the initial pH of 5.8.11 A similar to these results and presumably due to the 2,4-D presence, formic and
complete PCL degradation was obtained by Pereira et al.39 in chloride oxalic acids were the main subproducts of the PCL and 2,4-D degra-
media ([PCL]initial : 100 mg L–1 , NaCl 25 mM) after 150 min using dations in this study conducted on the TiNT-RuO2 electrocatalyst, al-
an initial pH = 6 and 30 mA cm–2 , although the toxic β-PbO2 was though it is important to note the differences in degradation techniques
used as the anode material. Of note, these experiments were similarly and electrocatalyst phase compared with the previous studies.
conducted in 0.05 M Na2 SO4 (plots not shown) without observing the According to the results shown above in terms of the active chlo-
PCL or 2,4-D degradations, which corroborated the absence of direct rine mechanism occurring between pH 5.8 (initial) and 4.6 (final) and
oxidation of these compounds on the electrode material. the recent studies conducted by our research group using DEMS,11
The evolutions of formic and oxalic acids were detected at 2.07 it is possible to propose the following reaction pathway over TiNT-
and 2.58 min of retention time, respectively, in the analysis of the RuO2 when HOCl predominates in solution (Fig. 8):
short chain carboxylic acids (refer to Electrochemical degradation via
active chlorine section). These intermediates are considered poten-
tially mineralizable compounds because the oxidation states of carbon RuOx + (H2 O)l → RuOx (H2 O)ads [1]
 
species (+II and +III, respectively) are close to CO2 , which should RuOx (H2 O)ads → RuOx e− − H O• ads + H + [2]
be achieved during the complete mineralization of PCL and 2,4-D.
• − −
This evaluation led to a slight change in the pH to more acidic con- RuOx − H O ads + Cl(aq) → RuOx (H OCl )ads + e [3a]
ditions (4.6 after 2 h) without influencing the HClO predominance
in the pH range from 3 to 6.10 Figure 7 shows the rapid increases in RuOx (HOCl)ads → RuOx + H OCl(aq) [4a]
both acids during the first 30 min of active chlorine production, fol- H OCl(aq) ↔ +ClO−
(aq)
+
pKa = 7.54
H(aq) [5a]
lowed by attenuated increases up to 120 min reaching concentrations  −  
of 58.04 and 24.84 mg L–1 , respectively. A. Ozcan et al. described RuOx e − H O• ads + H2 O → RuOx e− − O• ads + H + [3b]
the evolution of oxamic and glyoxylic acids in the early stages of PCL    
degradation by the electro-Fenton process and subsequent transforma- RuOx e− − O• ads + H2 O → RuOx e− − H OO• ads + H + [4b]
tions of the first two into oxalic and glycolic acids.40 However, D.A.C.    
Coledman et al.41 reported the formation of dichloroacetic and oxamic RuOx e− − H OO• ads → RuOx e− − O2ads + H + [5b]

Figure 7. Evolution of oxalic (squares) and formic (circles) acids concentra-

tion as a function of the treatment time with electrogenerated active chlorine Figure 8. Fraction of chloride species as a function of pH using a total con-
in 0.05 M NaCl (pH 5.8 and 25°C) on TiNTs-RuO2 at 10 mA cm−2 . centration of 0.05 M chloride.

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 Journal of The Electrochemical Society, 166 (15) H783-H790 (2019)
Figure 9. Chemical oxidation of 2,4-D and PCL (C0 = 144 and 30 mg L−1 ,
respectively) performed with 1 mol L−1 of hypochlorous acid. The experiment
was conducted at pH 5.8 and 25°C.
1 electrocatalyst for industrial applications by using a DC power supply.
MOx+1 → MOx + O2
2
where RuOx represents an active site on an oxygen atom of the
TiNT-RuO2 catalyst, (HOCl)ads is hypochlorous acid, (H O• ads ) is the
hydroxyl radical, (O• ads ) is the oxyl, and (H OO• ads ) is the peroxyl rad-
ical. The subscript “ads” denotes an adsorbed intermediate species on
the anode surface. Additionally, the oxygen evolution reaction (OER,
Reactions 3b–6b) concomitantly arises with the occurrence of active
chlorine (Reactions 3a–5a). The above mechanism presents two re-
markable connotations: pH dependence and electro-generated active
chlorine. The pH dictates the predominant active chlorine species on
the electrode surface and in the bulk solution, which is HOClads for
the range of pH (5.8 initially to 4.6 after 2 h of reaction) operating
during chloride electrolysis. This consideration is also based on the
thermodynamic diagram (fraction-pH) shown in Fig. 8 for the chlo-
ride concentrations we considered and the DEMS analysis reported
for this pH range.11 However, the activity of electro-generated active
chlorine (HOClads ) producing the PCL and 2,4-D degradations in Tor-
don 101 needs to be contrasted against the activity of soluble HOCl to
confirm in which state (adsorbed or soluble) the chlorine species is a
better oxidant. The first evidence is provided in Fig. 4, where no ox-
idants are shown to be produced in the absence of chloride oxidation
on the anode (Na2 SO4 ). However, Fig. 9 shows the control degrada-
tion tests conducted in 1 M of hypochlorous acid (pH = 5.8) used to
evaluate the elimination degree of the above compounds. Note that at
this pH, HOCl thermodynamically predominates in solution accord-
ing to the diagram in Fig. 8. As observed, the elimination of these
contaminants using soluble HOCl was not significant (i.e., lower than
30% for both pesticides) compared to the concentration decays shown
in Fig. 6 using electro-generated active chlorine (HOClads ), confirm-
ing the higher oxidizing power of the chlorine species formed over
TiNT-RuO2 . Additionally, no organic acids were detected during the
control test, indicating null mineralization in the presence of solu-
ble HOCl. Similar results were shown during the abatement of crys-
tal violet, which were considerably higher when active chlorine was
electro-generated on the electrode surface compared to those of the
addition of sodium hypochlorite to the solution with similar chloride
concentrations.5 The superior oxidizing activity found for the electro-
generated active chlorine (Fig. 6) against hypochlorous acid (Fig. 9)
during the degradations of PCL and 2,4-D confirmed the theoretical
proposal of the above reaction mechanism,6 wherein chloro and oxy-
chloro radicals “co-adsorbed” (HOClads ) on the anode surface play
important roles in the pollutant mineralization rather than the soluble
chlorine species.
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H789
Conclusions
A TiNT-RuO2 electrocatalyst was fabricated using a facile route in-
tended to catalyze the production of active chlorine to oxidize recalci-
trant organic compounds. During the first stage, Ti foils were anodized
at 70 V and subsequently annealed at 450°C in air to obtain crystalline
TiO2 NTs. A second stage was used to deposit a low content of Ru
on the TiO2 NTs via pulsed electrodeposition, followed by thermal
treatment. Metallic Ti and anatase were detected via XRD analysis of
the bare TiNTs. Similar signals were observed in the XRD pattern for
the TiNT-RuO2 with similar intensities, indicating a non-agglomerated
and well-dispersed coating of RuO2 nanoparticles. Additionally, peaks
associated with the tetragonal RuO2 structure were found for this cat-
alyst, which showed the structure of the anatase phase used as the
substrate. SEM images revealed the well-organized structure of the
TiNTs with an average inner diameter of approximately 185 nm, and
the RuO2 nanoparticles (size <10 nm) were regularly distributed on the
walls and around the mouths of the TiNTs. EDS analysis confirmed the
elements in the catalyst. Thus, this fabrication procedure renders a suit-
able method to consistently spread RuO2 nanoparticles on TiNTs with-
out clogging formation over their openings, while delivering mechan-
ical and structural integrity to the electrocatalyst via the support. Ad-
ditionally, it could also be more manageable to fabricate a TiNT-RuO2
[6b] The voltammograms recorded for the TiNTs in 0.05 M NaCl and
0.05 M Na2 SO4 showed that the pure NTs were not active for chloride
and H2 O oxidations, respectively, presumably because this material is
a poor electronic conductor. Activities toward these reactions were ob-
tained on the TiNT-RuO2 electrocatalyst, where the CER mechanism
preferentially occurred over the OER on the active sites connected
to RuO2 . EIS measurements corroborated these results because the
Nyquist spectra and the parameters obtained by fitting the experimen-
tal data showed a noticeable decay in the charge transfer resistance of
the TiNTs when coupled with the RuO2 nanoparticles. The estimation
of active chlorine production over this catalyst was confirmed during
electrolysis in NaCl via chemical analysis using iodometric titration.
Complete destruction of PCL was achieved within 2 h over TiNT-
RuO2 using 10 mA cm–2 in 0.05 M NaCl (pH 5.8), whereas 48% of 2,4-
D was abated under the same conditions. The generation of formic and
oxalic acids during the electrocatalytic oxidation confirmed the con-
version of the contaminants into potentially mineralizable compounds,
which were compared with the results from other reports where the de-
tection of similar byproducts was described. The control degradation
test carried out under the same conditions as above using 1 mol L–1 of
hypochlorous acid (soluble chlorine at pH = 5.8) showed that the elim-
ination of the contaminants did not exceed 30% for each case without
forming organic acids (null mineralization), confirming the higher ox-
idizing power of the active chlorine species formed over TiNT-RuO2 .
Acknowledgments
D. Elizarragaz and J.E. Carrera-Crespo thank CONACYT for
the economic support to pursue the Ph.D. and postdoctoral studies,
respectively. The authors acknowledge the facilities at UAM-A
for performing the XRD (Dr. Jorge Flores) and SEM (Dr. Rosa
Luna) analyses. Financial support was provided by SECITI-CDMX-
MEXICO (grant CM 8995c19 SECITI/2019), and CONACyT,
“Investigación Científica Básica” 2017-2018 grant No. A1-S-21608.
E.J. Ruiz received financial support from the PAICYT program of the
Universidad Autónoma de Nuevo León.
ORCID
J. Vazquez-Arenas https://orcid.org/0000-0001-8298-328X
E. J. Ruiz-Ruiz https://orcid.org/0000-0001-9524-7927
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