Journal of Electroanalytical Chemistry 873 (2020) 114438

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Journal of Electroanalytical Chemistry

journal homepage: www.elsevier.com/locate/jelechem

Electro- and photo-electrooxidation of 2,4,5-trichlorophenoxiacetic acid

(2,4,5-T) in aqueous media with PbO2, Sb-doped SnO2, BDD and TiO2-NTs
anodes: A comparative study
José Eudes L. Santos a, Dayanne C. de Moura b, Mónica Cerro-López c,
⁎
Marco A. Quiroz a, Carlos A. Martínez-Huitle a,d,
a
Universidade Federal do Rio Grande do Norte, Centro de Ciencias Exactas CCET – Institute of Chemistry, Lagoa Nova, CEP 59.072-970 Natal, RN, Brazil
b
Instituto de Educação Superior Presidente Kennedy (IFESP), Grupo Interdisciplinario de Cièncias, Lagoa Nova, CEP 59064-500 Natal, RN, Brazil
c
Universidad de las Américas Puebla, Departamento de Ciencias Químico Biológicas, Sta. Catarina Mártir, Cholula, Puebla, Mexico
d
Institut für Organische Chemie, Johannes Gutenberg-Universität Mainz, Duesbergweg 10-14, 55128 Mainz, Germany

A R T I C L E I N F O A B S T R A C T

Article history: In this work, the 2,4,5-T degradation in aqueous media was studied by electro- (EC) and photoelectrochemical (PEC) ox-
Received 16 February 2020 idation methods, which are two of the most important advanced oxidation processes (AOPs) for wastewater treatment.
Received in revised form 15 June 2020 Both EC and PEC experiments were carried out in a single compartment cell under galvanostatic conditions
Accepted 2 July 2020
(30 mA cm−2) at 298 K by using 0.05 M Na2SO4 + 200 ppm 2,4,5-T at pH 3 and pH 9, as model solutions. EC oxidation
Available online 10 July 2020
was performed using Sb-doped SnO2, PbO2 and boron doped diamond (BDD) as anodic materials. Besides these anodes,
Keywords:
TiO2 in a nanotubular structure (TiO2 NTs) with or without PbO2 dispersed nanoparticles (TiO2::PbO2) were also used for
Electrooxidation PEC oxidation process. In all cases, the electrolyzed solutions were periodically analyzed by UV–vis spectrophotometry
Phenoxy acetic acid (232 or 235 nm) and liquid chromatography (HPLC) for 2,4,5-T as well as the oxidation by-products. The mineralization
Herbicides level was occasionally measured by using total organic carbon (TOC). For PEC experiments the photocurrent response
SnO2 variations with potential in 0.5 M H2SO4 were obtained by the linear scanning voltammetry (LSV) method at a slow po-
PbO2 tential sweep (5 mV s−1). Results clearly showed that at 30 mA cm−2, the 2,4,5-T was 100% oxidized on Sb-doped SnO2
Si/BDD and 95% on PbO2 after 120 min of electrolysis, which allow to assume the EC as an adequate treatment method to re-
move this herbicide from wastewaters. HPLC results showed the formation of aromatic intermediates such as 2,4,5-
trichlorophenol (2,4,5-TCP) and 2,5-dihydroxyquinone (2,5-DHQ) followed by the formation of carboxylic acid such
as hydroxyacetic acid. For these cases, alkaline media (pH 9) was better than acidic media (pH 3) in about one magnitude
order in the apparent rate constant (k). On the other hand, photochemical activity results showed that PEC on TiO2-NTs::
PbO2 had higher photocurrent density values than on naked TiO2 NTs as photoanodes. These electrodes also had the bet-
ter photo conversion efficiencies (η), which strongly suggests the occurrence of a “co-catalysis” effect due to an electronic
transfer assisted by the closed contact between TiO2 and PbO2. This fact was supported by the PEC oxidation of 2,4,5-T in
aqueous solution, whose k value was slightly lower than that observed for bulk material.
© 2020 Elsevier B.V. All rights reserved.

1. Introduction
Nowadays, it is known that diseases such as cancer are caused by expo-
sure to certain kinds of chemicals. Among them, chlorophenols, in general,
and the chlorophenoxyacetic herbicides in particular. Phenoxy alkanoic
acids, such as 2,4,5-Trichlorophenoxyacetic acid (2,4,5-T) and 2,4-
Dichlorophenoxyacetic acid (2,4-D), are the most popular selective herbi-
cides against the weeds. Actually, 2,4-D is sold [1] with different
trademarked names, and when is mixed in equal parts with 2,4,5-T
produces the known Orange-Agent, one of the herbicides more strongly
used as defoliant of broad-leafed plants in the 70's decade. These herbicides
are also used in the saline form and as their derived esters or amines in
order to increase their solubility in water or oils as to be required [2], and
due to their action as auxin (plant hormone) are commonly denominated
as synthetic hormonal herbicides. Here, the attention point is because the
2,4,5-T always comes along with 2,3,7,8-Tetrachlorodibenzo-p-dioxin
(TCDD), a by-product of its manufacture, which is a high teratogenic
power dioxin very more toxic that 2,4,5-T itself. For this reason, in USA,

⁎ Corresponding author at: Universidade Federal do Rio Grande do Norte, Centro de Ciencias Exactas CCET – Institute of Chemistry, Lagoa Nova, CEP 59.072-970 Natal, RN, Brazil.
E-mail address: carlosmh@quimica.ufrn.br. (C.A. Martínez-Huitle).

http://dx.doi.org/10.1016/j.jelechem.2020.114438
1572-6657/© 2020 Elsevier B.V. All rights reserved.
J.E.L. Santos et al.
Canada, Sweden and other European countries this herbicide was forbid-
den to use in crops for human consumption; but in several other regions
it can still be used for some agricultural applications specially for weeds
combat. In any case, it is expected that underground water, rivers and
water reservoirs show variable levels of 2,4,5-T pollution through running
off or by infiltration as consequence of irrigation or washing processes of
crop fields or by discharge of industrial effluents. It must be clear that this
herbicide has been classified by the World Health Organization (WHO) as
a toxic compound type II with a maximum level of concentration permitted
of 100 ppb, therefore, its environmental impact should not be
underestimated and it must be considered as a priority target for elimina-
tion processes.
Owing to the global interest in water quality, all wastewater containing
organochlorine compounds, disregarding their origin, must be
decontaminated before its discharge to any natural water body or to biolog-
ical treatment plants. These kinds of effluents usually have low pH, high sa-
linity and also high toxicity levels, therefore, the decontamination process
to take into account must be at least one capable to transform the parental
organic compound in biocompatible compounds and, therefore, produce a
much less toxic residual water. In this sense, chemical and biological treat-
ment methods has been developed to remove persistent organic pollutants
(POP's) from wastewater by adsorption [3,4] and/or ozonation [5] pro-
cesses and by biochemical treatments as those reported by Lipthay et al.
[6] and by Huong et al. [7]. However, in all these methods drawbacks
have been observed that limit their applicability levels: biological (aerobic
culture) methods have usually long treatment periods (always that
chlorophenols are no present); physical methods could not remove POP's
at low concentrations (below 100 ppm); and some chemical methods
have low capacity rates. Meanwhile, the photolysis and photocatalytic op-
tions [8–13] are effective to remove POP's but very dependent on the oper-
ational conditions such as pH of solution, initial concentration of POP's,
intensity and nature of light, and mass and/or nature of catalytic material.
Among these alternative methods, the electrocatalytic approaches
based in the use of metallic oxides (of type MO2 e.g., PbO2, Sb-doped
SnO2 or IrO2) and boron doped diamond (BDD) as anodic materials stand
out. These electrocatalysts, in particular, have the prominent feature to pro-
duce one or more of highly reactive species such as hydroxyl radical (·OH),
superoxide anion (·O− 2 ), ozone (O3) and others which are generated by
water discharge on the electrode surface. Hydroxyl radical (·OH) is the
more powerful oxidizing agent (only after fluorine) in aqueous media
whose high oxidation potential (2.70 eV) [14] allows to produce a complete
mineralization of a variety of organic compounds, including
chlorophenoxyacetic pollutants [15,16]. This characteristic emphasizes
electrooxidation of organic compounds on these metal oxides and/or BDD
in aqueous media as really an advanced oxidation process (AOP's) [17,18].
In this context, Comninellis investigations demonstrated that efficiency
on partial or total oxidation of organic compounds depends on the pH solu-
tion, the applied current density and the anodic material used to produce
the free hydroxyl radicals [19]. For this last factor, the Comninellis model
classifies the anodic materials in two main groups: active and non-active elec-
trodes [20]. The basic difference between them is the interaction surface–
radical force, strong in the first and weak in the second case. This fact
makes possible a high interfacial concentration of very reactive ·OH radicals
capable to incinerate the organic pollutant according to the chemical
reaction [18]:
Mð•OHÞ þ R → M þ mCO2 þ nH2 O þ Hþ þ e− ð1Þ
where R is an organic compound with m carbon atoms and 2n hydrogen
atoms, without any heteroatom, which needs (2 m + n) oxygen atoms to
be totally mineralized to CO2. However, chemical Eq. (1) is not an isolated
reaction and competes with side reactions of M(·OH) like direct oxidation to
O2 from chemical reaction (2) or indirect consumption through dimeriza-
tion to hydrogen peroxide by chemical reaction (3):
Mð•OHÞ → M þ ½ O2 þ Hþ þ e− ð2Þ
2
Journal of Electroanalytical Chemistry 873 (2020) 114438
2 Mð•OHÞ→2 M þ H2 O2 ð3Þ
By this reason, the better anodic materials are those non-active elec-
trodes with a high overpotential for the oxygen evolution reaction (OER),
such as PbO2, SnO2, and their doped analogs. In this sense, BDD anodes
are currently the best non-active materials confirming this behavior
[18,21–24], being then proposed as the preferable electrode for treating or-
ganics by electrochemical oxidation [18,25]. In a recent work, the use of
metal-oxide-coated Ti electrodes to oxidize 2,4,5-T in water solutions was
reported [26]. For anodic materials, such as RuO2, SnO2-Sb and SnO2-Sb/
Ce-PbO2, the electrochemical treatment was examined at different pH con-
ditions and current density values, concluding that the anodic material
based on PbO2 was the most efficient to degrade 2,4,5-T (99.9%) and
with a 65.7% of capacity to remove TOC. These results are consistent
with the expectations for a non-active electrode.
As mentioned above, the oxidation of 2,4,5-T in aqueous media has also
been reported by using TiO2 as photocatalysts in suspension and light at
λ ≥ 340 nm [8,9], as well as by a flash photolysis method at 254/
266 nm [11]. But in both methods, the 2,4,5-T degradation followed a
very complex pathway by producing chlorinated aromatic intermediates,
some of which remained in water as undesirable by-products. The 2,4,5-T
oxidation by photocatalysis was clearly driven by the photogeneration of
·OH radicals at TiO2 in the 340–365 nm range of wavelength which acted
directly on the acetic radical of the 2,4,5-T to produce 2,4,5-trichlorophenyl
formate (2,4,5-TCF) and 2,4,5-trichlorophenol (2,4,5-TCP). However, the
subsequent formation of carboxylic acids prior to CO2 and H2O formation
was not described. On the other hand, the 2,4,5-T elimination by flash pho-
tolysis has a completely different degradation mechanisms. From this pro-
cess, it is interesting to observe here that the key steps are the cleavage of
C – Cl bonds by UV light followed by the hydroxylation at the correspond-
ing position in the benzene ring. However, the photolysis by-products are
not biocompatible to consider this as a safe wastewater treatment method.
Few studies about the 2,4,5-T degradation using photolysis, radiolysis,
or Fenton-type oxidation methods has also been published [27–30], even
when no attempts have been reported by using electro or photo-
electrochemical approaches. Therefore, the aim of this work is to study
the 2,4,5-T oxidation by AOP's using electrocatalytic and photo- electrocat-
alytic technologies in order to understand if the use of combined photo-
electro driving forces enhances the degradation and/or mineralization of
2,4,5-T in aqueous media. For this case, the most common photocatalyst
is titanium dioxide, TiO2, a semiconductor whose bandwidth ≥3.0 eV (de-
pending on the structure) demands the incidence of radiation of at least
365 nm to operate. Under lighting, this material generates charge carriers
that are highly active as long as there are reactive species capable of
using them; these are the photoelectrons housed in the conduction band
(e− +
BC), and the consequent vacancies (or gaps, hBV) that originate in the va-
lence band of the semiconductor. A reactive model of these charge carriers
is as follows (Eqs. (4)–(8)) [31]:
 
TiO2 þ hν → TiO2 e− þ
BC þ hBV ð4Þ
hþ • þ
BV þ H2 O → HO þ H þ e
−
ð5Þ
hþ
BV þ HO
−
→ HO• þ e− ð6Þ
hþ þ − • •
BV þ R → R þ e þ HO →P þ HO → ⋯ → xCO2 þ yH2 O ð7Þ
e− −
BC þ O2 → O2 ð8Þ
For photoelectrochemical experiments, two more limitations must be
considered: the conductivity of the anode material and its stability towards
corrosion, especially under lighting conditions. The n-TiO2 semiconductors,
as a surface or nanostructured layer on a Ti metallic base, have high con-
ductivity, are stable to corrosion, and are photoelectrochemically active
electrodes even when their bandwidth is inconvenient for direct use. But
J.E.L. Santos et al.
when combined with other oxides such as Fe, they can to form a solid solu-
tion that reduce bandwidth by up to one unit of eV (from 3.2 to 2.2 eV), or
with PbO2 they form a combination that induces synergistic effects that im-
prove the electronic transfer to the cathode.
Therefore, the electrooxidation process was carried out by using PbO2,
Sb-doped SnO2 and BDD working electrodes whereas for the
photoelectrooxidation approach, a TiO2 photoanode with nanotubular
structure of type Ti/TiO2-NTs (or Ti/TiO2-NTs::PbO2) [32] was used with
illumination at 365 nm. In all cases, the oxidation was developed as a func-
tion of 2,4,5-T solution pH (3 and 9) at a current density value of
30 mA cm−2.
2. Experimental
2.1. Chemicals
Ultrapure water (DI) was obtained by Simplicity water purification
(≈ 18 MΩ) system. Chemicals were of the highest quality commercially
available and were used without further purification. 2,4,5-
Trichlorophenoxy acetic acid (p.a. ≥ 99.5%), p-Nitrosodimethylaniline
(PNDA) (pure. p.a. ≥ 98.0%) and H2SO4 (puriss. p.a. 95–97%) were pur-
chased from Fluka. Titanium foil (99.7%, 0.25 mm thick) and Zirconium
foil (99.8%, 0.125 mm thick) were purchased from Aldrich, and Lead foil
(GR for analysis, 0.25 mm thick) from Merck. Glycerol (C3H8O3), sodium
fluoride (NaF), sodium sulfate (Na2SO4), acetone (C3H6O), ethanol
(C2H6O) and methanol (CH4O) were also purchased from Aldrich, all of
them as AR grade and used without any pretreatment. The model organic
compound solutions were prepared dissolving 200 mg of 2,4,5-T in a
0.05 M Na2SO4 pH 3.1 or pH 9.2 solution as supporting electrolyte, where
the pH value was adjusted by using 0.5 M H2SO4 or 0.1 M NaOH aqueous
solutions as required. A 200 ppm 2,4,5-T solution was used as a stock solu-
tion, from which the working solutions are prepared: 20 ppm (8 × 10−5 M)
for UV–vis spectrophotometry and first oxidation experiments; and
100 ppm for oxidation experiments with PbO2 and TiO2 NTs::PbO2 anodes.
2.2. Electrode material
The anodes were prepared as previously reported, however, a brief de-
scription of the preparation methods used here are immediately presented
with the corresponding bibliography.
PbO2 electrode was prepared growing the anodic oxide by applying
50 mA cm−2 during 1.5 h in a 10% H2SO4 solution at 25 °C, in order to ox-
idize the lead surface (3.4 cm2 of geometric surface area) into a brown film
Fig. 1. (a) SEM image of Ti anodized at 20 V for 2 h in a glycerol-DI water (1.3:1) mixture containing 0.5 wt% NaF and 0.2 M Na2SO4 and annealed at 500 °C. (b) SEM image
after PbO2 deposition from a 0.25 M Pb(NO3)2 + 0.125 M HNO3 solution at 50 mA cm2 during 10 s of electrolysis time. (c) XRD diffractogram for the PbO2 deposit on TiO2-
NTs array.
3
Journal of Electroanalytical Chemistry 873 (2020) 114438
of PbO2. More details concerning lead anode preparation and their charac-
terization are given elsewhere [21,33,34]. Sb-doped SnO2 electrodes
(6 cm2) were prepared by a sol-gel technique, which consisted of the fol-
lowing steps: a) preparation of precursor solutions (from SnCl4·4H2O and
SbCl3) b) precursor solution was onto a pre-treated titanium base and
dried at 50 °C. The whole process was repeated 10 times [19,35] after
which the coated Ti sheet was calcined at 500 °C. BDD films were provided
by CSEM (Neuchâtel, Switzerland) and synthetized on a conductive p-Si
substrate (1 mm, Siltronix) via a hot filament using the chemical vapor de-
position technique (HF-CVD) [36]. This procedure gave a columnar, ran-
domly textured, polycrystalline diamond film, with a thickness of about
1 μm and a resistivity of 15 mΩ cm (±30%) onto the conductive p-Si sub-
strate (2.6 cm2). TiO2 nanotube arrays (TiO2-NTs) were prepared by Ti an-
odization from 1 cm2 Ti sheets previously polished as follow: initially were
mechanically polished with No. 600 emery paper, 5 μm size alumina parti-
cles in water emulsion and ultrafine 3 μm abrasive paper, followed by a
thorough rinse with DI water and then degreased by a sequential ultrasonic
cleaning in acetone, methanol and DI water for 10 min each one and dried
under N2 gas flow. After cleaning treatment, the Ti sheets were anodized in
an electrolysis bath of glycerol and DI water mixed in a 1.3:1 volumetric
ratio containing 0.5 wt% NaF and 0.2 M Na2SO4. An electrochemical cell
with a two electrodes arrangement separated by approximately 1 cm was
used with a Zr sheet as the counter electrode. The electrochemical anodiza-
tion was carried out using a DC power supply (BK Precision model 1761) at
an applied voltage of 20 or 30 V during 240 min of anodization time. After
the anodic oxidation, the TiO2-NTs were washed with DI water to remove
the residual electrolyte and dried in a N2 stream. Finally, the Ti/TiO2-NTs
plates were annealed at 500 °C for 1.5 h by using a heating rate of
5 °C min−1. These TiO2-NTs interfaces were then used to deposit PbO2 in
order to get the photoelectrochemical anodic material (TiO2-NTs::PbO2)
used in this work (2.1 cm2). For this, an electrolytic process was carried
out in a 0.25 M Pb(NO3)2 + 0.125 M HNO3 solution by using a galvanosta-
tic method (Biologic 150 model Potentiostat-Galvanostat) at an applied cur-
rent density of 50 mA cm−2 (of geometrical area) during 5, 10 or 15 s of
electrolysis time depending the coverage level required [32].
2.3. Physical characterization of the TiO2-NTs::PbO2 anode
2.3.1. Morphologic analysis
The morphology of the Ti/TiO2-NTs and Ti/TiO2-NTs::PbO2 anodes was
determined by scanning electron microscopy (SEM) under similar condi-
tions as reported in a previous work [32]. Thus, Fig. 1a shows the
nanotubular structure (TiO2-NTs) obtained after the processes of
J.E.L. Santos et al.
anodization and annealed of the Ti sheet, also is shown in Fig. 1b the
nanoflower structure of the PbO2 deposited on the TiO2-NTs array to
form the TiO2-NTs::PbO2 anode. In addition, the XRD analysis (Fig. 1c) con-
firmed a β-type structure for the PbO2 deposit that is known as the most
electrochemically active.
2.3.2. Photocurrent and photoconversion efficiency curves
The photoactivity of the Ti/TiO2-NTs and the Ti/TiO2-NTs::PbO2 an-
odes was determined by means of the photocurrent density curves which
were obtained using a linear sweep voltammetry technique at a low scan
rate (5 mVs−1) in both dark and illuminated conditions, however, it was
observed that the dark photocurrent densities values were negligible.
Therefore, Fig. 2 shows only the photocurrent density (mA cm−2) values
for the illuminated condition (blue line) at a λ = 365 nm. From these
data of photocurrent density (mA cm−2), the photoconversion efficiency
(η) from light energy to chemical energy in the presence of an applied po-
tential as estimated in [37,38] is also shown in Fig. 2 (red line). As can be
observed, a maximum value of η ~ 9% was obtained at a minimum applied
potential of 0.08 V/MSE, just to the potential value where the photocurrent
density saturation was reached.
2.4. Electrochemical (EC) and photoelectrochemical (PEC) experiments
2.4.1. Oxidation of p-Nitrosodimethylaniline (PNDA)
Since the ability of an anodic material to oxidize the organic compounds
is related to their capacity to produce ·OH radicals, it is important then to
verify that they really act as an active source of ·OH radicals under the
real conditions of electrolysis. For this, the production of ·OH radicals by
water discharge, reaction (9),
H2 O → •OH þ Hþ þ e− ð9Þ
was confirmed by the bleaching of p-Nitrosodimethylaniline solutions due
to the reaction (10) [39,40].
ð10Þ
PNDA can be spectrophotometrically traced at 350 nm at pH 3 and
440 nm at pH 9; moreover, it is not electroactive with respect to anodic ox-
idation and it exhibits high reaction rates with the ·OH radicals (from [41],
κ = 1.25 × 1010 M−1 s−1 for ethanol). For this work, a detailed study was
carried out at the PbO2 and TiO2-NTs::PbO2 electrodes (as a test), during
the electrolysis of 0.05 M Na2SO4 + 2 × 10−5 M PNDA (pH 9) solutions
at 30 mA cm−2 and 298 K. During the electrolysis time for PNDA discolor-
ation, the corresponding UV spectrum was obtained at about 5 min inter-
vals. Additionally, for the TiO2-NTs::PbO2 electrode, an illumination of
365 nm during all electrolysis time was used. In both cases, the UV–vis
(200–500 nm) spectrum was recorded at certain sampled times of
bleaching PNDA reaction.
4
Journal of Electroanalytical Chemistry 873 (2020) 114438
Fig. 2. Photocurrent density (mA cm−2) (blue line) and photoconversion efficiency
(% η) (red line) as a function of the applied potential (vs. MSE) for a TiO2-NTs::PbO2
anode. Illumination conditions were at a λ = 365 nm with a light power of
1.4 mW cm−2. Potential was changed at a sweep rate of 5 mV s−1 in 0.5 M H2SO4.
2.4.2. Oxidation of 2,4,5-Trichlorophenoxyacetic acid (2,4,5-T)
The oxidation experiments were carried out in single compartment cells
under galvanostatic conditions (30 mA cm−2) by using Sb-doped SnO2,
PbO2 and Si/BDD as working electrodes for EC oxidation and with a
TiO2-NTs::PbO2 anode for PEC experiments, all of them in 8 × 10−5 M
2,4,5-T + 0.05 M Na2SO4 solutions (pH 3 and/or pH 9). In all cases, an
ultra-high-purity graphite rod (EG&G PARC) or a Pt mesh was used as cath-
ode whereas a Hg/Hg2SO4/K2SO4(sat) (MSE: 0.616 V vs NHE) was used as
the reference electrode. The temperature of the electrolyte was fixed at
25 °C and kept constant by using a water thermostat, also the stirring rate
was kept almost constant (350 ± 50 rpm) by using a magnetic stirrer. Dur-
ing electrolysis, 0.3 mL samples were withdrawn to monitor model com-
pound decay through UV–vis spectrophotometry (232 nm at pH 3 and
235 nm at pH 9) and by HPLC analysis. Final reaction products were ana-
lyzed through HPLC. The HPLC analysis for aromatic compounds was per-
formed with an Inertsil ODS 3, 5 μm, 4.6 × 150 mm Chromatographic
Column at 25 °C with a mobile phase of Acetonitrile:Water:Acetic Acid,
49:49:2 at a flow rate of 0.8 mL min−1 and a detection wavelength of
288 nm. The HPLC analysis for carboxylic acids was performed with a PL-
Hyplex H 8 μm, 7.7 × 300 mm Chromatographic Column at 35 °C with a
mobile phase of 4 mM H2SO4 in DI water at a flow rate of 0.4 mL min−1
and a detection wavelength of 210 nm. For PEC experiments the photocur-
rent response variations with potential in 0.5 M H2SO4 were obtained by
the linear scanning voltammetry (LSV) method at a slow potential sweep
(5 mV s−1). Experiments under controlled light illumination were carried
out using a 100 W high-intensity long wave UV lamp (Black-Ray model B
100AP), which produces 365 nm UV light of an irradiation intensity of
6.0–9.0 mW cm−2. The electrochemical cell was a three-electrode
(100 mL capacity) jacketed cell specially designed to develop photochemi-
cal tests without reflection losses by windows. Here, the TiO2-NTs::PbO2
electrode was used as the photoanode. Total organic carbon (TOC) was
only obtained for the initial and the final electrolyzed solutions by using a
Shimadzu Model TOC-L CSH/CSN.
3. Results and discussion
3.1. UV spectroscopic characteristics of 2,4,5-T in aqueous media
The UV spectra of 0.05 M Na2SO4 + 8 × 10−5 M 2,4,5-T solutions
(pH 9) exhibit three absorption bands at 206, 235 and 292 nm, being
these values associated to the ‘B, ‘La and benzenoid absorption bands, re-
spectively (Fig. 3). Owing to the strong substitution of the benzene ring as
J.E.L. Santos et al. Journal of Electroanalytical Chemistry 873 (2020) 114438

Fig. 3. UV absorption spectra of 0.05 M Na2SO4 + x mg L−1 2,4,5-T solutions as a function of 2,4,5-T concentration, 0 < x ≤ 22 mg L−1. Insert: Beer's law applied to each one
of absorption bands observed: ▲ 206 nm; ● 235 nm; ■ 292 nm.

well as to the influence of the aqueous media used as solvent, a apparent rate constant (k) values must be associated with a greater or lesser
bathochromic shift was observed regards to typical wavelength values re- availability of ·OH radicals in solution. As previously discussed, in the non-
ported for unsubstituted benzene [42,43]. Fig. 3a shows UV spectra of active anodes the concentration of ·OH radical at the interfacial region de-
2,4,5-T as a function of 2,4,5-T concentration as well as the corresponding pends on the strength at which they are physically adsorbed after the elec-
Beer's law applied to each absorption band observed (Fig. 3b) and for which tronic transfer from their formation reaction (9) [23].
the following molar absorptivity (ε) values were calculated: ε292 = 1891,
ε235 = 6387 and ε206 = 51,096 L mol−1 cm−1. From these results, we 3.3. Electro- and photo- electrooxidation of 2,4,5-T at BDD, Sb-doped SnO2,
have chosen the wavelength at 235 nm as those at which quantitative anal- PbO2 and TiO2-NTs::PbO2 anodes
ysis of 2,4,5-T would be performed since Beer's law is not completely
obeyed at 206 nm and the absorption band at 292 nm shows to be very Previous works related to the electrooxidation of organic compounds
small for quantitative purposes. have shown that 30 mA cm−2 is a good compromise between a fast oxida-
tion rate and a low effect on surface stability of electrocatalysts; mainly for
3.2. Bleaching of p-Nitrosodimethylaniline (PNDA) solutions as indicator of the PbO2 anodes that at lower or higher current density values, are not very ef-
anodic ·OH production fective for oxidation or undergo surface corrosion. Therefore, all 2,4,5-T
electro-oxidation experiments were carried out at an applied current den-
The production of ·OH radicals at metallic oxide of MO2 (M = Sn or Pb) sity of 30 mA cm−2 in aqueous media at pH 3 or pH 9 and at room
type is a well-known fact reported in literature under different experimen- temperature.
tal conditions [20]. However, when a new or modified anodic material is
introduced as electrocatalysts to oxidize organic compounds, it is conve- 3.3.1. Electrooxidation of 2,4,5-T on anodes of MO2 type and BDD
nient to prove their capacity to produce ·OH radicals regarding an anodic The first interesting aspect to observe is the similar UV behavior, this is,
reference material such as the Pb/PbO2 electrode. Thus, the ability of the all 2,4,5-T electrochemical systems shows the same general UV profile with
Ti/TiO2-NTs::PbO2 anode to produce ·OH radicals was tested in relation
to the Pb/PbO2 anode at the same electrochemical conditions, that is, at
30 mA cm−2 in alkaline media (pH 9) where the PNDA bleaching process
was spectrophotometrically monitored at 440 nm (inset of Fig. 4). As can
be observed in Fig. 4 the PNDA bleaching rate on the TiO2-NTs::PbO2
anode (k = 0.217 min−1) is almost tenfold higher than on the Pb/PbO2
anode (k = 0.0296 min−1), both of them at pH 9. This could be an expected
result if we take into account only the effect of increasing surface area due
to the PbO2 dispersion on the nanotubular TiO2 support. However, owing
to the illumination conditions of the TiO2-NTs::PbO2 anode, it could be pos-
sible to have a complementary contribution by photoactivity due to the
semiconductor TiO2 behavior. A co-catalytic effect [44] between TiO2-NTs
and PbO2 has previously been reported by us for the methyl red discolor-
ation [32]. In any case, all anodic materials used in this research are active
to produce ·OH radicals, the apparent rate constants at 440 nm and
30 mA cm−2 in alkaline media for Sb-doped SnO2 and BDD were
0.0125 min−1 and 0.0483 min−1, respectively.
These results confirm that all material used as anodes are active to pro-
duce ·OH radicals, but also that the PNDA bleaching reaction takes place in
solution as a pseudo-first order reaction in [PNDA] [45]. This fact means
that the PNDA bleaching reaction is either independent of the concentra- Fig. 4. Discoloration curves of PNDA as measured at 440 nm for: Ti/TiO2-NTs::
tion of ·OH radicals or that the ·OH concentration is in a large excess and re- PbO2, and Pb/PbO2 electrodes. Insert: UV absorption spectra of a 0.05 M
mains constant during the electrocatalytic reaction. According to the Na2SO4 + 1.8 × 10−5 M PNDA solution (pH 9) as a function of the electrolysis
reaction (10) the first assumption is not feasible since just the ·OH radicals time on a Ti/TiO2-NTs::PbO2 electrode under illumination conditions at 365 nm
are the responsible species for the PNDA discoloration. Therefore, the and an applied current density of 30 mA cm−2.

5
J.E.L. Santos et al. Journal of Electroanalytical Chemistry 873 (2020) 114438

three well defined absorbance band at 206, 232 and 288 nm for 2,4,5-T in
acidic media (pH 3) and 206, 235 and 292 nm in alkaline media (pH 9).
This fact is shown in Fig. 5 (a to c) for the 2,4,5-T electrooxidation at
30 mA cm−2 and pH 9. This behavior suggests that, in a first instance, the
electrooxidation of 2,4,5-T occurs through a similar degradation route
which was supported by HPLC analysis of the electrolyzed solutions as de-
scribed in the experimental section. The HPLC results showed the presence
of two main oxidation by-products: 2,4,5-Trichlorophenol (2,4,5-TCP) and
2-hydroxyethanoic acid (2-HEA); both of them produced by the first hy-
droxylation step of the 2,4,5-T molecule, Eq. (11). In this case, the 2,4,5-
TCP was considered because there was not chromatographic evidence of
the formation of the 2,4,5-Trichloroformate compound.
type of OP treated. In this case, the structural and electronic characteristics
of the SnO2 anode doped with Sb provided an electrocatalytic activity sim-
ilar to that observed for BDD. From the Stucky's works [46,47], it has been
shown that the presence of Sb in the crystal structure of SnO2 allows a good
electrical conductivity and increases the oxygen overpotential to values of
approximately 2.4 V/MSE (with respect to the value of ~1.5 V/MSE from
Pt) at 30 mA cm−2. This fact means that the Sb-doped SnO2 anode has
not only a good ability to generate ·OH radicals from the water discharge
[20], but it also promotes that the ·OH radicals have a longer residence
time on its surface and; therefore, a greater oxygen transfer capacity to-
wards the OP for its oxidation [48]. Due to this behavior, the 2,4,5-T

ð11Þ

Additionally, the HPLC analysis of carboxylic acids also showed the

adsorbed on the surface of the anode rapidly reacts with the ·OH radicals
presence of maleic (MAc) and oxalic (OAc) acids, which can only come
and converts into 2,4,5-TCP, just as observed in the HPLC analysis from
from the hydroxylation and opening of the aromatic ring according to the
the solution within the first minutes of electrolysis. Taking into account
chemical scheme (12),

ð12Þ

It is feasible that the degradation continues until the eventual minerali-

the modifications to the structure of the SnO2 surface, originated by the
zation to CO2 and H2O as it has been evidenced for phenols
substitution of Sn+4 ions by the Sb+3 and Sb+5 ions [49,50], and the elec-
electrooxidation. It was also observed that, although all anodic materials
tronic environment that the Sb+3 ions acquire (including the presence of a
used are capable to remove 2,4,5-T by applying 30 mA cm−2 where the al-
pair of electrochemically active lone electrons [49]); we would expect that
kaline media (pH 9.2) was usually better than acidic media (pH 3.1). This is
Sb-doped SnO2 anode to be better or equally efficient than the BDD anode
shown in Fig. 6, where the degradation percentage of 2,4,5-T was plotted as
for the first oxidation step of 2,4,5-T. The UV spectrophotometry data and
a function of the electrolysis time. The kinetic analysis of the concentration
HPLC results support this assumption. Conversely, PbO2 anode did not
results obtained from the absorbance data at 232 (pH 3.1) and 235 (pH 9.2)
show significant changes in its electrocatalytic properties when compared
nm is consistent with a pseudo-first-order model for the degradation of
to the oxidation of other organic compounds, even simpler ones such as
2,4,5-T in aqueous solution, as shown in Table 1 where the estimated values
phenol [51]. In this work, Duan et al. [51], reported a degradation effi-
of apparent kinetic constants are summarized. These results show that these
ciency of 44% at 30 mA cm−2 after 60 min of electrolysis time. It was
anodic materials are efficient electrocatalysts to degrade an OP as stable as
established that the reaction follows a pseudo-first-order kinetics, with an
2,4,5-T, especially the SnO2 anode doped with Sb.
apparent rate constant of 0.011 cm−1 at the same applied current density.
Although it is common to find that the BDD anodes exhibit the best elec-
Therefore, it can be suggested that the electrochemical oxidation of 2,4,5-T
trochemical degradation efficiency, this feature usually depends also on the

Fig. 5. UV absorption spectra of 0.05 M Na2SO4 + 8 × 10−5 M 2,4,5-T solutions at pH 9 as a function of the electrolysis time at a) PbO2, b) Sb-doped SnO2 and c) Si/BDD
anodes.

6
J.E.L. Santos et al. Journal of Electroanalytical Chemistry 873 (2020) 114438

Table 1
Kinetic results of the electrochemical oxidation of 2,4,5-T at BDD, PbO2 and Sb-
doped SnO2 anodes from aqueous media at pH values of 3.1 and 9.2. Electrolysis
carried out at 30 mA cm−2, 298 K and 350 ± 50 rpm.
pH 9.2 pH 3.1

BDD PbO2 SnO2 BDD PbO2 SnO2

k (min−1) 0.0169 0.0121 0.0554 0.0246 0.0065 0.0494

R2 0.9798 0.9906 0.9984 0.9946 0.9500 0.9933
% deg 83 88 91 80 65 94
at t(min) 124 120 60 70 90 60

% deg. = degradation percentage, at t (min) = at time (min), k = apparent kinetic

constant.

electrocatalytic performances in comparison with TiO2-NTs::PbO2 elec-

trode, see Fig. 7a.
After 240 min, the concentration of 2,4,5-T decreased about 80% on
Pb/PbO2 electrode, while a 99% of 2,4,5-T removal was achieved when
TiO2-NTs::PbO2 was used. In Fig. 7a is observed that both anodes presented

Fig. 6. Degradation percentage of 2,4,5-T from 0.05 M Na2SO4 + 8 × 10−5 M

2,4,5-T solutions at a) pH 9.2 and b) pH 3.1 as a function of the electrolysis time.
Electrolysis was carried out at an applied current density of 30 mA cm−2, 298 K
and under magnetic stirring (350 ± 50 rpm). Percentage values were estimated
from the corresponding absorbance values.

at the anodes here studied occurs through a three-stage degradation

scheme as proposed by Polcaro et al. [52]: (i) oxidation of 2,4,5-T to
2,4,5-TCP, (ii) opening of the aromatic ring to form carboxylic acids and,
(iii) mineralization of the carboxylic acids to carbon dioxide.

3.3.2. Photoelectrooxidation of 2,4,5-T on a Ti/TiO2-NTs::PbO2 anode

It was shown in Fig. 4 that PbO2 dispersed on a TiO2-NTs surface has a
better electrocatalytic activity for the discoloration of PNDA solutions that
the PbO2 anode directly formed by anodization of a Pb sheet in acidic
media. These results were explained assuming the existence of a co-
catalytic effect between TiO2 and PbO2 which is activated under the illumi-
nation conditions of the photo-electro-catalytic process [32]. In this way,
the TiO2-NTs::PbO2 anode become more efficient to produce ·OH radicals
and, hence, more capable of degrading OP content in wastewaters. There-
fore, in order to validate this last assumption, oxidation of 2,4,5-T was car-
ried out using both a TiO2-NTs::PbO2 anode and a Pb/PbO2 anode in a
0.2 M Na2SO4 model solution to which 100 ppm of 2,4,5-T was added.
The concentration of supporting electrolyte was chosen to better solubilize Fig. 7. a) 2,4,5-T degradation from 0.2 M Na2SO4 + 100 ppm 2,4,5-T solutions by
the amount of 2,4,5-T acid used. For these experiments, electrochemical ox- using a Pb/PbO2 anode and a TiO2-NTs::PbO2 anode under illumination at a λ =
idation was carried out by applying 40 mA cm−2, and the concentration of 365 nm with a light power of 1.4 mW cm−2 as a function of the electrolysis time.
2,4,5-T was monitored by HPLC analysis of the electrolyzed solution. For Applied current density of 40 mA cm−2, 298 K and under magnetic stirring
(350 ± 50 rpm). b) Pseudo-first order approximation (ln([2,4,5-T]) vs t) with its
the case of the TiO2-NTs::PbO2 anode, the electrooxidation experiments
associated kinetic data. [2,4,5-T] values were calculated from the corresponding
were performed under illumination at a λ = 365 nm with a light power
HPLC data.
of 1.4 mW cm−2. Results showed that, Pb/PbO2 anode achieved lower

7
J.E.L. Santos et al.
Fig. 8. Variation in the composition of some oxidation products identified by HPLC,
as a function of electrolysis time. The 0.2 M Na2SO4 + 100 ppm 2,4,5-T solution
was electrolyzed by using a TiO2-NTs::PbO2 anode under illumination at a λ =
365 nm with a light power of 1.4 mW cm−2 at an applied current density of
40 mA cm−2, 298 K and under magnetic stirring (350 ± 50 rpm). Concentration
data are given as relative areas of the HPLC peaks for comparison purposes only.
No calculation of mass balance was made. Legend of lines: unknown compounds
(UCx), Oxalic acid (OxAc), Maleic Acid (MAc) and 2,4,5-Trichlorophenol (245TCP).
a similar behavior towards the 2,4,5-T degradation from the aqueous solu-
tion, however, the kinetics of the oxidation process seems not follow the
same behavior. Fig. 7b shows that at Pb/PbO2, 2,4,5-T degradation was
well-fitted to a pseudo-first order reaction into all electrolysis time interval
with an apparent rate constant of 0.0072 min−1, but for the case of
Ti/TiO2-NTs::PbO2 electrode, the reaction takes place by two stages as elec-
trolysis time increases: one of them between 0 and 120 min with an appar-
ent rate constant of 0.0109 min−1, and the other between 120 and 240 min
with an apparent rate constant of 0.025 min−1. According to the results of
absorbance and HPLC, it is possible to propose that the first stage is identi-
fied with the chemical Eq. (6) and the second with the chemical Eq. (7). In
the first stage, the slower one, the ·OH radicals react with the 2,4,5-T
adsorbed to produce the 2,4,5-TCP and the 2-HEA, and as soon as the
2,4,5-TCP is formed, this is hydrolyzed by the ·OH radicals accumulated
in the electrode/solution interface and transformed into the corresponding
carboxylic acids [53]. HPLC analysis showed, in a general way, how the
composition of the solution advances during the first 150 min of electrolysis
(Fig. 8). This behavior could be attributed to a co-catalytic effect [44] orig-
inated by the interaction between the nanoflowers of PbO2 and the nano-
structured TiO2 surface. In our previous work [54], it was suggested that
high adsorption in the first stage is clearly influenced by the nanostructured
surface of both materials. It was also demonstrated that the higher oxida-
tion rates for electrocatalysis under illumination were due to an increased
photoconversion efficiency attributed to the PbO2 high metallic character
that favors the electronic transfer through the nanotubular structure of
the TiO2 towards the cathode. In this way the charge recombination (h+
and e) inside the TiO2 during the illumination is diminished, and therefore,
oxidation processes on the TiO2-NTs::PbO2 surface are improved [32].
4. Conclusions
The results of electrochemical oxidation of 2,4,5-T on PbO2, Sb-doped
SnO2 and BDD anodes have clearly shown that the organic compound can
be degraded to the formation of carboxylic acids in a relatively short elec-
trolysis time. The degradation forms, initially 2,4,5-TCP, an intermediate
compound in which the majority of published works on the subject coincide
and, after the opening of the aromatic ring, the corresponding carboxylic
acids are formed. All three anodes degraded the 2,4,5-T well, although a
8
Journal of Electroanalytical Chemistry 873 (2020) 114438
better electrocatalytic activity was observed for the Sb-doped anode
SnO2, as verified by the comparison of kinetic data in Table 1. The result
has been explained based on the structural and electronic characteristics
that are produced by the substitution of the Sn+4 ions for the Sb+5 and
Sb+3 ions in the doping process of SnO2 with Sb. The expansion of the
unit cell of SnO2 and the presence of a pair of solitary electrons around
the ion Sb+3, confer unique electrocatalytic properties to the Sb-doped
SnO2, as demonstrated by its capacity to produce ·OH radicals by water dis-
charge, and to adsorb the organic molecule in a better position for its
oxidation.
On the other hand, it has been possible to confirm that the oxidative ca-
pacity of a photocatalytic material such as TiO2 can be improved by com-
bining it with another material that may or may not show photoactivity.
By dispersing PbO2 in the nanotubular array of TiO2, a structure of the
type TiO2-NTs::PbO2 is formed that improves the transport of electrons
through the oxide layer towards the cathode; it decreases the recombina-
tion rate of charges (h+- e) in the illumination, and it modifies the kinetics
of the oxidation stages of 2,4,5-T. It can be suggested, then, that PbO2, in its
nanoflower structure, acts as a co-catalyst that improves the photoactivity
of TiO2, in its nanotubular array.
Declaration of Competing Interest
The authors declare that they have no known competing financial inter-
ests or personal relationships that could have appeared to influence the
work reported in this paper.
Acknowledgments
Financial supports from Conselho Nacional de Desenvolvimento Cien-
tífico e Tecnológico (Brazil) are gratefully acknowledged (CNPq –
439344/2018-2), as well as the support from Fundação de Amparo à
Pesquisa do Estado de São Paulo (Brazil) with the FAPESP Project 2014/
50945-4. Carlos A. Martínez-Huitle acknowledges the funding provided
by the Alexander von Humboldt Foundation (Germany) and Coordenação
de Aperfeiçoamento de Pessoal de Nível Superior (Brazil) as a Humboldt
fellowship for Experienced Researcher (88881.136108/2017-01) at the
Johannes Gutenberg-Universität Mainz, Germany.
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