Journal of Electroanalytical Chemistry 767 (2016) 40–48

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Journal of Electroanalytical Chemistry

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

Use of a carbon felt–iron oxide air-diffusion cathode for the

mineralization of Malachite Green dye by heterogeneous electro-Fenton
and UVA photoelectro-Fenton processes
Orlando García-Rodríguez a, Jennifer A. Bañuelos b, Abdellatif El-Ghenymy c, Luis A. Godínez a,
Enric Brillas c,⁎, Francisco J. Rodríguez-Valadez a,⁎
a
Centro de Investigación y Desarrollo Tecnológico en Electroquímica, Parque Tecnológico Qro Sanfandila, P.O. Box 76703, Pedro Escobedo, Querétaro, Mexico
b
Centro de Innovación Aplicada en Tecnologías Competitivas, Departamento de Investigación y Posgrado, Omega 201, Fraccionamiento Industrial Delta, P.O. Box 37545, León, Guanajuato, Mexico
c
Laboratori d'Electroquímica dels Materials i del Medi Ambient, Departament de Química Física, Facultat de Química, Universitat de Barcelona, Martí i Franquès 1-11, 08028 Barcelona, Spain

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

Article history: A novel carbon felt cathode coated with iron oxides has been prepared by Fe3+ electrodeposition. The deposited
Received 20 November 2015 iron content was analyzed by X-ray fluorescence, the composition of iron oxides formed by X-ray diffraction and
Received in revised form 17 January 2016 the morphology of deposits by scanning electron microscopy and energy-dispersive X-ray spectroscopy. Freshly
Accepted 19 January 2016
prepared electrodes were used as air-diffusion cathodes in a stirred tank reactor with a boron-doped diamond
Available online 1 February 2016
(BDD) anode to degrade solutions of Malachite Green dye at pH 3.0 by heterogeneous electro-Fenton (EF) and
Keywords:
photoelectro-Fenton (PEF) processes. Oxidizing agents were hydroxyl radicals formed at the BDD surface from
Carbon felt–iron oxide cathode water oxidation and at the cathode surface or in the bulk from Fenton's reaction between deposited or leached
Heterogeneous electro-Fenton Fe2+ and electrogenerated H2O2 in both treatments, along with the photo-oxidation by UVA light in heteroge-
Heterogeneous photoelectro-Fenton neous PEF. The decolorization and mineralization of dye solutions were faster for the latter process due to
Malachite Green the photolysis of Fe(III) complexes with initial oxalate and generated carboxylic acids. TOC decay always obeyed
Water treatment a pseudo-first-order kinetics. The increase in dye concentration decelerated the decolorization efficiency
and mineralization rate, but enhanced the mineralization current efficiency. A test of 10 consecutive cycles of
heterogeneous EF treatment of 50 mg L−1 of Malachite Green at 21.7 mA cm−2 showed a gradual loss of iron
oxides from the cathode with decreasing dye mineralization rate. An improvement of the stability of the novel
cathode is then necessary for its reuse with a better keeping of the oxidation power of heterogeneous EF and
PEF treatments of organic pollutants in waters.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction wastewaters have several advantages such as their high efficiency,

Recently, there is a growing interest in the remediation of waste-
waters contaminated with biorecalcitrant and/or toxic organics, like
dyes, by advanced oxidation processes (AOPs). These methods include
a large variety of environmentally friendly methods with the common
feature of the in situ generation of hydroxyl radical (•OH) [1–3]. This
radical is the second strongest oxidant known after fluorine and its
great standard reduction potential (E°(•OH/H2O) = 2.80 V/SHE) allows
its non-selective reaction with most organics until total mineralization,
i.e., overall transformation into carbon dioxide and inorganic ions. In
this context, electrochemical AOPs (EAOPs) emerge as a good alterna-
tive to carry out the on-site generation of this radical for wastewater
treatment [4–6]. The electrochemical methods for the treatment of
⁎ Corresponding authors.
E-mail addresses: brillas@ub.edu (E. Brillas), frodriguez@cideteq.mx
(F.J. Rodríguez-Valadez).
URL: http://www.cideteq.mx (F.J. Rodríguez-Valadez).
mild operating conditions, ease of automation, versatility, and low
cost, especially when they are powered by renewable energy from
wind and solar sources [7].
The most common EAOP is anodic oxidation (AO), also known as
electrochemical oxidation. In AO, an undivided cell is utilized with a
high O2-overvoltage anode (M) having the ability of generating oxidiz-
ing physisorbed hydroxyl radical (M(•OH)) as intermediate from water
discharge to O2 at high enough current density (j) via reaction (1)
[8–11]:
M þ H2 O → Mð•OHÞ þ Hþ þ e− : ð1Þ
The preferred anode for AO is the boron doped diamond (BDD) thin-
film electrode, since it has much greater overvoltage for O2 release than
other conventional anodes like Pt and PbO2 [8,12,13]. This is feasible
because of the very weak interaction between •OH and BDD surface
that promotes the mineralization of organics in waters [14–16]. An

http://dx.doi.org/10.1016/j.jelechem.2016.01.035
1572-6657/© 2016 Elsevier B.V. All rights reserved.
 O. García-Rodríguez et al. / Journal of Electroanalytical Chemistry 767 (2016) 40–48
alternative method is AO with electrogenerated H2O2 (AO-H2O2), in
which this species is continuously produced from O2 reduction usually
at a carbonaceous cathode as follows [11]:
O2ðgÞ þ 2Hþ þ 2e− → H2 O2 :
Reaction (2) is very effective for cathodes such as carbon felt [13,
17–20], carbon sponge [21], activated graphite carbon [22,23], carbon
nanotubes [24,25], carbon–polytetrafluoroethylene (PTFE) gas (O2 or
air) diffusion [12,26–29] and BDD [30,31]. Reactive oxygen species
(ROS) such as pre-eminently M(•OH), along with H2O2 and its anodic
product the hydroperoxyl radical (HO2•) in smaller proportion, are the
oxidizing species acting to remove organics in AO-H2O2.
Our laboratories are interested in the development of EAOPs like
electro-Fenton (EF) and photoelectro-Fenton (PEF) based on the addi-
tion of a catalytic amount of Fe2+ to the solution to enhance the oxida-
tion ability of generated H2O2 by the production of Fe3 + and •OH in
the bulk from Fenton's reaction (3) [5,22,32–36]. The homogeneous EF
process involves the organic oxidation primordially by both M(•OH)
and •OH radicals, with an optimum pH near 3 [37]. This method is
clearly advantageous compared with the classical Fenton reagent be-
cause the catalytic reaction (3) can be continuously accelerated by
Fe2+ regeneration from Fe3+ reduction by H2O2 or at the cathode via
reactions (4) and (5), respectively [3,38–40].
Fe2þ þ H2 O2 þ Hþ →Fe3þ þ •OH þ H2 O
Fe3þ þ H2 O2 þ Hþ →Fe2þ þ HO2 • þ H2 O
Fe3þ þ e− →Fe2þ
However, the formation of short-linear carboxylic acid as final prod-
ucts inhibits the mineralization process in homogeneous EF since they
form Fe(III) complexes that are hardly destroyed by hydroxyl radicals
[9,11,40]. This drawback can be overcame using the homogeneous PEF
process, in which the solution is simultaneously irradiated with an
UVA light to photodecompose the Fe(III)–carboxylate complexes by
reaction (6) [12,26,27,29]. Moreover, UVA radiation can induce the
regeneration of more Fe2+ with production of •OH thanks to the photol-
ysis of Fe(OH)2+ species present in solution from reaction (7) [5,34].
FeðOOCRÞ2þ þ hv → Fe2þ þ CO2 þ R•
FeðOHÞ2þ þ hv → Fe2þ þ •OH
A drawback of the homogeneous EF process is the need of the neu-
tralization of the final treated solution, usually with formation of large
amounts of iron sludge, whose disposal is expensive and difficult [41].
Several authors have tried to solve this disadvantage by reducing the
quantity of dissolved iron species using heterogeneous EF. In this way,
there is little information about the use of carbonaceous cathodes
with deposited iron oxides and their oxidation ability for this EAOP.
There have only been reports on the preparation of graphite felt [42]
and activated carbon felt [43] cathodes coated with iron oxides to decol-
orize a 5 mg L−1 Rhodamine B dye solution in a divided cell under air
bubbling through the solution. These cathodes release small quantities
of iron species to the solution and oxidant •OH is generated in the
bulk from Fenton's reaction (3) as well as on the electrode surface
from a similar heterogeneous reaction. However, the use of air-
diffusion cathodes covered with iron oxides has not been previously
proposed, despite that it is well-known the larger ability of these elec-
trodes to electrogenerate H2O2 [3,9,11].
This paper presents the preparation of a novel carbon felt–iron oxide
electrode by Fe3 + electrodeposition and its application to decolorize
and mineralize solutions of Malachite Green (also called Basic Green
41
4) dye by heterogeneous EF and PEF. The trials were performed in an
undivided electrolytic cell with a BDD anode and the above carbon
felt–iron oxide electrode as air-diffusion cathode. The Fe deposited in
the novel electrode, its morphological structure, its performance to gen-
ð2Þ erate H2O2 and the losses of iron in consecutive cycles of treatment were
examined. Malachite Green has been chosen as a model of triphenyl-
methane dye, commonly used for the dyeing of cotton, silk, paper, and
leather and in manufacturing of paints and printing inks [38]. It is exten-
sively utilized as biocide in the aquaculture industry due to its effective-
ness and relatively low cost against important protozoal and fungal
organisms [44,45]. However, Malachite Green is toxic to human cells,
might cause liver tumor formation and poses a serious risk to aquatic
life [46]. Several papers have described its degradation by conventional
methods, including biological treatments [47,48], sunlight radiation
[49] and sonochemical degradation [50], as well as by AOPs like TiO2
photocatalysis [51], Fenton [52], photo-Fenton [52,53], zero-valent
iron [54] and homogeneous EF [38,39].
2. Experimental
2.1. Chemicals
Malachite Green (83% purity as oxalate salt, C52H54N4O12, C.I. 42000)
was supplied by Sigma-Aldrich and used as received. Anhydrous sodi-
um sulfate used as background electrolyte was of analytical grade
ð3Þ purchased from Fluka. Ferrous sulfate heptahydrate and ferric chloride
hexahydrate were of analytical grade purchased from Merck. All the so-
ð4Þ lutions were prepared with high-purity water produced by a Millipore®
Milli-Q system (18.2 MΩ cm resistivity at 25 °C). Their initial pH was
ð5Þ adjusted to 3.0 with analytical grade sulfuric acid supplied by Merck.
2.2. Preparation of the carbon felt–iron oxide cathode
The carbon felt–iron oxide electrodes were prepared by Fe3+ elec-
trodeposition. To do this, the bare carbon felt material provided by
Grupo Roe (Mexico) was firstly sonicated for 2 h in 0.1 M H2SO4. This
step was done to increase the surface oxygen functionalities on carbon
[36]. A circle of 3 cm2 of the above material was then introduced as
the working electrode in a three-electrode conventional cell, which
contained 100 mL of 0.1 M H2SO4 as the supporting electrolyte, a Pt
rod as the auxiliary electrode and a double junction Ag|AgCl|KCl(sat)
(0.199 V/SHE at 25 °C) as the reference electrode. The solution was
ð6Þ deaerated by bubbling pure N2 for 60 min and further, 2 mL of 5 mM
FeCl3 as iron precursor was added to it. The electrodeposition on the ex-
ð7Þ ternal face of the carbon felt was made by adding again 2 mL of 5 mM
FeCl3 to the solution each hour upon application of a constant cathodic
potential of −1.100 V for 3 h using an Ecochemie Autolab PGSTAT100
potentiostat–galvanostat, commanded by NOVA 1.5 software.
2.3. Electrochemical assays
Fig. 1 illustrates a sketch of the experimental set-up utilized for the
heterogeneous EF and PEF degradations of Malachite Green solutions.
The cell was an open, one-compartment cylindrical glass tank reactor
of 150 mL capacity. It was surrounded with an external jacket where
thermostated water circulated to keep the solution temperature at
25 °C. The volume of the treated solutions was 100 mL and they were
vigorously stirred by means of a magnetic bar at 800 rpm to ensure
homogenization and transport of reactants toward/from the electrodes.
A 3 cm2 BDD thin-film electrode provided by NeoCoat (La-Chaux-de-
Fonds, Switzerland) was used as the anode and a 3 cm2 bare carbon
felt or carbon felt–iron oxide electrode was used as air-diffusion cath-
ode. Both electrodes were separated near 1 cm. The cathode was placed
at the bottom of a cylindrical holder of polypropylene (see Fig. 1) with
an inner nickel screen of 125 meshes as current collector in contact
with a Ni/Cr wire as electrical connection. It was fed with an air flow
42 O. García-Rodríguez et al. / Journal of Electroanalytical Chemistry 767 (2016) 40–48
Fig. 1. Sketch of the electrochemical system used for the heterogeneous electro-Fenton
(EF) and photoelectro-Fenton (PEF) treatments of Malachite Green solutions. (1) 3 cm2
carbon felt–iron oxide air-diffusion cathode, (2) 3 cm2 boron-doped diamond (BDD)
anode, (3) Ni/Cr wire electrical connection, (4) air flow, (5) magnetic bar, (6) water
from thermostat at 25 °C, (7) water to thermostat at 25 °C, (8) solution and (9) 6 W
UVA lamp for PEF experiments.
rate of 20 mL min−1 for H2O2 electrogeneration from reaction (2). The
assays were performed at constant j provided by an Amel 2053
potentiostat–galvanostat. In the heterogeneous PEF trials, a Philips TL
6-W black light blue tube lamp was placed 5 cm above the solution to
supply an UVA radiation centered at λmax = 360 nm, with an average
power density of 5 W m− 2, measured with a Kipp&Zonen CUV 5 UV
radiometer. The impurities of the BDD anode surface were previously
cleaned by polarization in 100 mL of a 0.05 M Na2SO4 solution at
pH 3.0 and 100 mA cm−2 for 240 min.
2.4. Analytical determinations
The solution pH was determined with a Crison GLP 22 pH-meter.
Prior to analysis, the samples withdrawn from treated solutions were
neutralized to stop the degradation process and filtered with Whatman
0.45 μm PTFE filters. Hydrogen peroxide concentration was determined
by measuring the light absorption of the titanic–hydrogen peroxide
complex at λ = 408 nm with a Unicam 1800 UV–Vis spectrophotome-
ter [55]. The loss in color of the dye solutions was monitored from the
absorbance decay at the maximum dye wavelength λmax = 616 nm
using the above spectrophotometer and with 1:10 diluted samples.
The decolorization efficiency or percentage of color removal was then
obtained from the following equation [3,9]:
A0 −At
Color removal ð%Þ ¼  100 ð8Þ
A0
where A0 and At denote the absorbance of the starting solution and at
time t of electrolysis, respectively.
The mineralization of Malachite Green solutions was followed from
the abatement of their total organic carbon (TOC), measured with a
Shimadzu VCSN TOC analyzer. Aliquots of 50 μL were injected into the
above analyzer and reproducible TOC values (accuracy = ±1%) were
determined. Ion chromatography analysis of electrolyzed solutions
−
allowed obtaining the concentrations of released NH+ 4 and NO3 ions
using the procedures reported elsewhere [29].
The comparative oxidation power of heterogeneous EF and PEF pro-
cesses was better explained from the mineralization current efficiency
(MCE), estimated for each treated solution at a given electrolysis time
t (h) by Eq. (9) [12]:
n FV s ΔðTOCÞ exp
MCEð%Þ ¼  100 ð9Þ
4:32  107 m I t
where F is the Faraday constant (96,487 C mol−1), Vs is the solution vol-
ume (L), △(TOC)exp is the experimental TOC decay (mg L−1), 4.32 × 107
is a conversion factor (3600 s h−1 × 12,000 mg C mol− 1), m is the
number of carbon atoms of the molecule (52 in our case), I is the applied
current (A) and t is the electrolysis time (h). The number n of electrons
consumed in the mineralization process was 226 assuming the overall
conversion of Malachite Green into carbon dioxide and ammonium
ion, as will be discussed below, as follows:
C52 H54 N4 O12 þ 92H2 O → 52CO2 þ 4NHþ þ −
4 þ 222H þ 226e : ð10Þ
The surface morphology of the bare carbon felt and the prepared
carbon felt–iron oxide cathodes was examined by scanning electron
microscopy (SEM) using a JEOL-5400LV system. An accelerating voltage
of 15 keV was used for the SEM measurements and for scanning and
mapping by energy-dispersive X-ray spectroscopy (EDS). The X-ray dif-
fraction (XRD) patterns were obtained using a Bruker-AXS D8 Advanced
X-ray diffractometer system with Cu Kα (λ = 1.5406 Å) radiation. Scans
were recorded in the 2θ angle range between 20 and 70° with a step size
of 0.040° and a power of 40 kV and 30 mA. X-ray fluorescence (XRF)
measurements were made with the carbon-felt coated with iron oxides
using a SHIMADZU XRF-1800 device in order to quantify iron concen-
trations as mass percentages.
3. Results and discussion
3.1. Characterization of the carbon felt–iron oxide electrode
The electrodeposition of iron over the carbon felt material was firstly
corroborated from XRF analysis. These measurements revealed the
presence of about 1.525 g Fe per kg C in the fresh electrode. They
were carried out again after 360 min of heterogeneous EF treatment of
a 50 mg L− 1 Malachite Green solution in 0.050 M Na2SO4 at pH 3.0,
25 °C and 21.7 mA cm−2, as well as after 10 cycles of the same degrada-
tion process, always using the same carbon felt–iron oxide air-diffusion
cathode. After the first cycle of treatment, near 1.372 g Fe per kg C was
obtained, whereas this value was strongly reduced to 0.399 g Fe per kg C
after 10 cycles. This means that each treatment involved an average loss
of about 0.12 g Fe per kg C, indicating that in heterogeneous EF and PEF
processes, the production of •OH is expected to take place in both, the
bulk and the cathode surface via homogeneous and heterogeneous
Fenton's reaction (3) [42,43].
The XRD patterns for the carbon felt–iron oxide cathode before
and after its use in the heterogeneous EF treatment of 50 mg L− 1 of
Malachite Green at 21.7 mA cm−2 are depicted in graphics a and b of
Fig. 2, respectively. In both cases, these results evidence the presence
of iron oxides such as magnetite, with characteristic crystallographic
(311), (511) and (400) planes at 35.2°, 56.9° and 43.1°, respectively,
and maghemite, with a marked crystallographic (220) plane at 30°, as
reported in other works [56–59]. Note that in the freshly prepared
 O. García-Rodríguez et al. / Journal of Electroanalytical Chemistry 767 (2016) 40–48
Fig. 2. X-ray diffraction pattern of the carbon felt–iron oxide electrode (a) before and
(b) after the heterogeneous EF treatment of 100 mL of a 50 mg L−1 Malachite Green
solution in 0.050 M Na2SO4 at pH 3.0, 25 °C and 21.7 mA cm−2 for 360 min. (c) X-ray
diffraction pattern of the bare carbon felt electrode.
electrode (see graphic a of Fig. 3), a peak at 44.8° related to zero-valent
iron (110) plane was also found [60], which disappeared after carrying
out the heterogeneous EF degradation of the dye (see graphic b of
Fig. 2). The presence of Fe metal on the coated carbon felt suggests the
formation of iron oxides as main products of the corrosion of the iron
particles deposited. In contrast, a small broad peak at 25° also appeared
in the XRD pattern of the used cathode (see graphic b of Fig. 2), which
can be ascribed to the (002) plane of the hexagonal graphitic structure
of the carbon material [36,61]. The fact that this peak at 25° was not
detected neither in the fresh electrode (see graphic a of Fig. 2) nor in
Fig. 3. SEM images of carbon felt coated with iron oxide (a) before and (b) after the heterogeneous EF degradation reported in Fig. 2. Elemental mapping profile from EDS of Fe Kα (c) before
and (d) after the above EF process.
43
the bare carbon felt material (see graphic c of Fig. 2), suggests that the
layer structure related to this peak in the two latter cases was covered
by impurities and the hydroxyl radicals acting in the heterogeneous EF
process cleaned the cathode surface recovering the ordered crystalline
graphitic structure.
SEM analysis of the same fresh and used carbon felt–iron oxide elec-
trodes was further made to study the morphological properties of the
deposit. Fig. 3a exemplifies a SEM image obtained for a fresh electrode.
It can be observed that iron oxides formed agglomerates uniformly
spread over the carbon felt, with a large amount of ravines on the sur-
face. The same morphology can be seen in Fig. 3b for the same electrode
once used for 360 min as air-diffusion cathode in the heterogeneous EF
of 50 mg L−1 of Malachite Green at 21.7 mA cm−2. In this case, however,
the ravines on the fibers were not so marked, probably due to the partial
loss of iron oxides, as stated above from XRF measurements.
The elemental mapping profiles for Fe Kα of the same electrodes, re-
corded by EDS and presented in Fig. 3c and d, corroborated the presence
of iron over the carbon fibers as well as their distribution patterns. Thus,
a better distribution with larger agglomerates of iron can be observed
for the fresh electrode (see Fig. 3c), whereas the attenuation of the red
areas in the used cathode (see Fig. 3d) is indicative of a drop in iron con-
centration due to its loss during the heterogeneous EF process.
3.2. H2O2 production by the carbon felt–iron oxide cathode
To assess the H2O2 production in the electrolytic system, previous
tests were made with 100 mL of a 0.050 M Na2SO4 solution at pH 3.0
and 25 °C using the cell equipped with the BDD anode and the bare
carbon-felt air-diffusion cathode by applying a j range between 11.7
and 33.3 mA cm−2 for 240 min. In these experiments, a gradual accu-
mulation of H2O2 up to a steady-state content in solution was always
observed, without changing the solution pH, which is a common behav-
ior for electrolytic cells with air-diffusion cathodes [3,11]. Fig. 4 illus-
trates this trend for the best performance obtained at 21.7 mA cm−2,
attaining a maximum steady H2O2 concentration of 94 mg L−1.
44 O. García-Rodríguez et al. / Journal of Electroanalytical Chemistry 767 (2016) 40–48

Fig. 4. Concentration of accumulated H2O2 vs. electrolysis time found for 100 mL of
0.050 M Na2SO4 at pH 3.0 and 25 °C using a stirring tank reactor with a BDD anode at
21.7 mA cm−2. Air-diffusion cathode: ( ) bare carbon felt and (■) carbon felt coated
with iron oxide.

The steady state for H2O2 accumulation was reached just when its
electrogeneration rate from reaction (2) became equal to its destruction
one, which mainly takes place by its oxidation at the BDD anode to O2
gas with generation of HO2• as intermediate via reactions (11) and
(12) [62]:

H2 O2 → HO2 • þ Hþ þ e− ð11Þ

HO2 • → O2ðgÞ þ Hþ þ e− : ð12Þ

From the aforementioned findings, a j = 21.7 mA cm−2 was taken

for all the subsequent assays carried out with the same cell equipped
with a fresh carbon felt–iron oxide air-diffusion cathode. Under these
conditions, Fig. 4 highlights a much smaller and rapid H2O2 accumula-
tion, only up to 4.3 mg L−1, by electrolyzing the 0.050 M Na2SO4 solu-
tion at pH 3.0. The high decay in H2O2 accumulation when using a
freshly prepared carbon felt coated with iron oxides compared with
that of the bare carbon felt, can be explained by the fast consumption
of this species by Fe2 + from Fenton's reaction (3), which can occur
either heterogeneously at the iron oxides deposited onto the cathode
surface or homogeneously in the bulk with the soluble iron species
released from the cathode during electrolysis [3,42]. The quick steady
state achieved for H2O2 in the medium operating with the carbon felt–
iron oxide cathode suggests the existence of a constant •OH generation
from both, the heterogeneous and homogeneous Fenton's reaction (3).
3.3. Degradation of Malachite Green solutions by heterogeneous EF and PEF
The oxidative power of the heterogeneous EF and PEF methods, as
well as the role of generated hydroxyl radicals and UVA light, was
ascertained by studying the decolorization and mineralization of solu-
tions with 50–150 mg L−1 Malachite Green treated in the BDD/carbon
felt–iron oxide cell at the optimum j of 21.7 mA cm−2 for 360 min. In
these runs, a freshly prepared cathode was always initially utilized
and it was found that the starting pH of 3.0 remained practically
unchanged during all the treatments.
Fig. 5a and b evidences a slower loss in solution color with increasing
dye content, although faster decolorization was always achieved for
the heterogeneous PEF than heterogeneous EF under comparable condi-
tions. Thus, total decolorization was found after about 60, 75 and 90 min
of the former EAOP and close to 75, 90 and 105 min of the second one at
Fig. 5. Variation of the percentage of color removal with electrolysis time for (a) the
heterogeneous EF and (b) heterogeneous PEF treatments of 100 mL of Malachite Green
solutions in 0.050 M Na2SO4 at pH 3.0 and 25 °C using a BDD/carbon felt–iron oxide cell
at 21.7 mA cm−2. Dye concentration: ( ) 50 mg L−1, ( ) 100 mg L−1 and (■)
150 mg L−1.
growing Malachite Green concentrations of 50, 100 and 150 mg L−1,
respectively. The quicker loss in color for each treatment as dye concen-
tration decayed can be simply associated with the destruction of a larger
proportion of organic load with a similar quantity of BDD(•OH) and •OH
generated at the same j of 21.7 mA cm−2 [11]. The superiority of the
heterogeneous PEF for decolorization can be explained by the oxalate
charge present in the commercial dye. This species can form Fe(III)–
oxalate species in the bulk that can be rapidly photodecarboxylated
via reaction (6) regenerating more Fe2+ with the consequent increase
in •OH production from homogeneous Fenton's reaction (3), thereby
enhancing Malachite Green oxidation. It is also noteworthy that most
color (74–95%) was lost in the first 15 min of electrolysis (see Fig. 5a
and b), whereas the decolorization rate was strongly decreased at
longer time. This suggests the formation of colored aromatic products
that absorb at wavelengths near to the λmax = 616 nm of the starting
dye as well and that are more slowly destroyed by generated hydroxyl
radicals, as previously reported for homogeneous EF and PEF degrada-
tions of azo dye solutions [5,29,34].
The mineralization of the products formed during Malachite Green
degradation in the above EAOPs was monitored from the normalized
TOC abatement with electrolysis time and the results obtained are
 O. García-Rodríguez et al. / Journal of Electroanalytical Chemistry 767 (2016) 40–48
Fig. 6. Change of normalized TOC with electrolysis time for the trials of Fig. 5.
(a) Heterogeneous EF and (b) heterogeneous PEF processes at 21.7 mA cm−2. Malachite
Green concentration: ( ) 50 mg L−1, ( ) 100 mg L−1 and (■) 150 mg L−1.
shown in Fig. 6a and b for the heterogeneous EF and PEF processes, re-
spectively. While the mineralization rate always decreased with rising
initial dye content, the relative oxidation power of the EAOPs increased
in the order EF b PEF in all cases. For heterogeneous EF, TOC was more
poorly reduced by 85%, 76% and 69% after 360 min of electrolysis at
50, 100 and 150 mg L−1 of Malachite Green, respectively (see Fig. 6a),
whereas for heterogeneous PEF, the analogous trials led to final TOC
removals of 98%, 87% and 77% (see Fig. 6b). The progressive loss in nor-
malized TOC reduction as organic load rose can be attributed again to
the lower reaction rate of similar amounts of generated hydroxyl radi-
cals (BDD(•OH) and •OH) to oxidize greater quantities of intermediates
formed. The higher mineralization power of PEF can be related to the
additional acceleration of the destruction of many products in solution
upon the photo-oxidation of UVA irradiation. This is the case, for exam-
ple, of the Fe(III) complexes of carboxylic acids formed from Malachite
Green degradation [39], which can be quickly photolyzed by reaction
(6), but very difficultly removed by hydroxyl radicals under EF condi-
tions [9].
On the other hand, the final electrolyzed solution of the 50 mg L−1
Malachite Green solution was analyzed by ion chromatography
45
showing that its initial N was mineralized as 83% of NH+ 4 ion and 13%
of NO− +
3 ions. This means that NH4 was the pre-eminent ion lost during
the EAOPs, as stated in the overall mineralization reaction (10).
3.4. Kinetics and current efficiency for the mineralization process
The exponential decay of normalized TOC for all the curves of Fig. 6a
and b was well fitted to a pseudo-first-order kinetic model by plotting ln
(TOC0/TOC) vs. time, where TOC0 and TOC represent the solution TOC
before electrolysis and after a time t. This behavior presupposes that a
constant amount of BDD(•OH) and •OH is available to attack the
organics during each run, limiting the kinetics of TOC abatement in
both treatments [11]. From this analysis, the apparent rate constant
for TOC removal (kTOC), with the corresponding square of regression co-
efficient (R2), was determined for each trial. For 50, 100 and 150 mg L−1
of Malachite Green, decreasing kTOC values of 6.1 × 10−3 min−1 (R2 =
0.997), 5.0 × 10−3 min−1 (R2 = 0.995) and 4.4 × 10−3 min−1 (R2 =
0.981) were obtained for heterogeneous EF, respectively, whereas, as
expected, higher kTOC values of 8.7 × 10− 3 min− 1 (R2 = 0.987),
5.9 × 10−3 min−1 (R2 = 0.981) and 4.8 × 10−3 min−1 (R2 = 0.987)
were found for the analogous heterogeneous PEF assays. Since the
kTOC ratio between the latter and former processes dropped from 1.36
for 50 mg L−1 to 1.09 for 150 mg L−1, one can conclude that the photol-
ysis of UVA light in heterogeneous PEF becomes more effective for more
diluted solutions, probably because this radiation destroys more rapidly
the lower amounts of photoactive products formed.
The oxidation ability of the EAOPs was better clarified from the MCE
values of the above trials calculated from Eq. (9) and presented in Fig. 7a
and b. It should be noted that in the heterogeneous EF process, a maxi-
mum current efficiency of 200% can be reached, 100% due to the anodic
contribution from BDD(•OH) formation via reaction (1) and another
100% as a result of •OH production from cathodically generated H2O2
by reactions (2) and (3). However, for the heterogeneous PEF process,
much higher MCE values can be obtained because the action of UVA
light on the degradation process is not considered in Eq. (9). Fig. 7a
and b shows that maximum current efficiencies were always obtained
at the beginning of both EAOPs, with values from 154% to 179% for het-
erogeneous EF and even much greater, from 230% to 360%, for the more
powerful heterogeneous PEF. These MCE values are much superior than
those usually determined for the analogous homogeneous EAOPs of azo
dyes [5,29,34], suggesting a well-efficient destruction of organics by •OH
at the surface of the iron oxides coating on the carbon felt cathode. An
inspection of Fig. 7a and b also highlights a gradual growth in MCE as
the dye content rose in both heterogeneous EAOPs. This tendency is
not surprising because more amount of TOC (in mg L−1) was abated
for greater amounts of Malachite Green, conversely the lower drop of
normalized TOC (see Fig. 6a and b). Although the same amounts of
BDD(•OH) and •OH are generated at the same applied j, the presence
of higher organic load enhances their reaction with these radicals in det-
riment to the waste non-oxidizing reactions of radicals. This is a typical
phenomenon also observed in homogeneous EF and PEF [3]. These
waste reactions include the oxidation of BDD(•OH) to O2 by reaction
(13) and the consumption of •OH with H2O2 and Fe2 + by reactions
(14) and (15), respectively [9,11]:
2BDDð•OHÞ → 2BDD þ O2 þ 2Hþ þ 2e− ð13Þ
H2 O2 þ •OH → HO2 • þ H2 O ð14Þ
Fe2þ þ •OH → Fe3þ þ OH− : ð15Þ
Moreover, the MCE value for each treatment of Fig. 7a and b
underwent a dramatic fall with prolonging electrolysis. This general
46 O. García-Rodríguez et al. / Journal of Electroanalytical Chemistry 767 (2016) 40–48

energy source in the SPEF process [26,34], the energy cost related to
the use of the artificial UVA lamp was not taken into account.
As can be seen in Fig. 8, the EC value decreased with increasing
Malachite Green from 50 to 150 mg L−1, as expected from the concom-
itant increase in MCE (see Fig. 7b). At 15 min, the energy consumption
only varied between 0.01 and 0.09 kWh g−1 TOC, but at longer time it
increased rapidly up to final values of 2.92, 1.46 and 0.97 kWh g−1
TOC for initial concentrations of 50, 100 and 150 mg L−1, respectively.
This trend can be ascribed to the progressive loss of organic matter
and the generation of more recalcitrant intermediates. This confirms
the fast mineralization of the organic matter with high degradation
rate and current efficiency and low energy cost at short times, whereas
the slower destruction of more recalcitrant products causes a decelera-
tion of the process at long times with loss of MCE and greater EC.
The above findings evidence the best viability of the degradation of
more concentrated dye solutions by PEF. Although the mineralization
takes place in smaller extent with increasing organic concentration,
lower EC values are obtained due to the greater current efficiency.

3.6. Stability of the carbon felt–iron oxide electrode during heterogeneous

EF treatment

The stability and activity of iron oxides are key parameters for the
reusability of coated carbon felt cathodes in heterogeneous EAOPs.
XRF analysis of a cathode after 360 min of heterogeneous EF of a
50 mg L−1 Malachite Green solution at 21.7 mA cm− 2 revealed the
partial loss of the iron deposit (see Section 3.1). For a better evaluation
of the electrode stability, the same assay was repeated up to 10 cycles
for the same cathode. Fig. 9a shows that the percentage of TOC removal
at the end of the heterogeneous EF processes decreased from 85% for the
first cycle to 68% for the tenth cycle. The TOC decay in the consecutive
electrolysis always obeyed a pseudo-first-order kinetics and the corre-
sponding kTOC values, presented in Fig. 9b, also dropped slightly
and gradually with enlarging cycles of treatment. This loss in activity
of the carbon felt–iron oxide cathode suggests a significant deceleration
of •OH production from heterogeneous Fenton's reaction (3) at the elec-
trode surface upon its repetitive usage. This suggestion agrees with the
large release of deposited iron after 10 cycles of treatment, as detected
by XRF (see Section 3.1). In each cycle, it is then expected the dissolution
Fig. 7. Mineralization current efficiency calculated from Eq. (9) vs. electrolysis time for the
of a similar content of iron oxides in the solution of pH 3.0, thereby
experiments shown in Fig. 6. (a) Heterogeneous EF and (b) heterogeneous PEF treatments
at 21.7 mA cm−2. Malachite Green content: ( ) 50 mg L−1, ( ) 100 mg L−1 and (■)
150 mg L−1.

trend can be related to the progressive decay in organic charge of the

medium along with the formation of more persistent products [8].
The results obtained in this work evidence that the more powerful
heterogeneous PEF process is able to yield an almost total mineraliza-
tion with 98% TOC removal for a 50 mg L−1 Malachite Green solution
treated at 21.7 mA cm−2. Nevertheless, this EAOP is able to mineralize
more concentrated dye solutions in smaller extent, but with higher
current efficiency.

3.5. Energy consumption

The main operational cost of EAOPs is related to the electrical energy

consumption. The energy consumption (EC) was then calculated for the
more efficient PEF process as follows [9]:

Ecell I t
Energy Cost EC kWh g−1 TOC ¼ ð16Þ
V s ΔðTOCÞ exp
Fig. 8. Energy consumption calculated from Eq. (16) vs. electrolysis time for the PEF
where Ecell is the average potential difference of the cell (in V). Since the experiments shown in Fig. 6. Malachite Green content: ( ) 50 mg L−1, ( ) 100 mg L−1
UVA lamp in PEF can be replaced by sunlight as a renewable and free and (■) 150 mg L−1.
 O. García-Rodríguez et al. / Journal of Electroanalytical Chemistry 767 (2016) 40–48
Fig. 9. (a) Percentage of TOC removal after each cycle of heterogeneous EF degradation of
100 mL of Malachite Green solutions in 0.050 M Na2SO4 at pH 3.0 and 25 °C using the same
BDD/carbon felt–iron oxide cell at 21.7 mA cm−2 for 360 min. (b) Apparent rate constant
for TOC removal for each of the above trials.
generating analogous amounts of •OH from homogeneous Fenton's re-
action (3), but the presence of less iron onto the carbon felt inhibits
the production of this radical at the cathode surface. Despite this, our
results evidence that the consecutive dye degradation occurred almost
as quickly as the first cycle without any oxidation delay. More efforts
are needed to prepare more stable carbon felt electrodes coated with
iron oxides in order to better keep their activity and to enhance their
reusability in heterogeneous EAOPs.
4. Conclusions
It has been shown the viability of carbon felt coated with iron oxides
as air-diffusion cathode for the heterogeneous EF and PEF degradations
of Malachite Green solutions at pH 3.0. In these EAOPs, organics are
oxidized by BDD(•OH) along with •OH formed from Fenton's reaction
at the cathode surface or in the bulk from released iron species, and/or
the photolytic action of UVA irradiation. The decolorization and miner-
alization of dye solutions were much faster for heterogeneous PEF
under comparable conditions. The superiority of this EAOP was ex-
plained by the formation of Fe(III) complexes in solution with oxalate
present in the commercial dye as well as with short-chain carboxylic
acids produced during dye degradation. The quick photolysis of these
47
species by UVA light in heterogeneous PEF regenerated more soluble
Fe2+, accelerating •OH production from homogeneous Fenton's reaction
and enhancing the oxidation process. An increase in dye concentration
in both EAOPs caused lower decolorization efficiency and normalized
TOC decay, but with higher current mineralization due to the decelera-
tion of waste reactions of hydroxyl radicals. The TOC abatement always
obeyed a pseudo-first-order kinetics. An almost total mineralization
with 98% TOC removal was obtained for the most powerful heteroge-
neous PEF process of a 50 mg L− 1 Malachite Green solution at
21.7 mA cm− 2. Consecutive 10 cycles of treatment of this solution
under heterogeneous EF conditions revealed a gradual loss in oxidation
ability as a result of the continuous leaching of iron oxides from the
cathode, mainly decelerating the heterogeneous Fenton's reaction.
This was confirmed from XRF, XRD, SEM and EDS analyses of the cath-
odes after and before use. More efforts are then needed to improve
the stability of carbon felt–iron oxide electrodes to enhance their
reusability in heterogeneous EAOPs.
Acknowledgments
The authors are grateful to F.M. Rivas Esquivel for the XRD analysis,
F. Espejel Ayala for the SEM–EDX technical assistance and F. López
García for his collaboration in the illustration of this work. The authors
acknowledge the financial support from CONACyT (Mexico) under
project 106590 and from MINECO (Spain) under project CTQ2013-
48897-C2-1-R, cofinanced with FEDER funds.
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