Microelectronic Engineering 149 (2016) 3136

Contents lists available at ScienceDirect

Microelectronic Engineering
journal homepage: www.elsevier.com/locate/mee

An analytical study of the electrochemical degradation of methyl orange

using a novel polymer disk electrode
Hayat Abdulla Yusuf a,, Zainab Mohammed Redha a, Sara J. Baldock c, Peter R. Fielden b, Nick.J. Goddard c
a
b
c

Department of Chemical Engineering, College of Engineering, University of Bahrain, P.O. Box 32038, Manama, Bahrain
Chemistry Department, Faraday Building, Lancaster University, Bailrigg, Lancaster LA1 4YB, United Kingdom
School of Chemical Engineering and Analytical Science, The University of Manchester, Manchester M60 1QD, United Kingdom

a r t i c l e

i n f o

Article history:
Received 18 March 2015
Received in revised form 12 August 2015
Accepted 8 September 2015
Available online 12 September 2015
Keywords:
Degradation
Azo dyes
Methyl orange
Polymer electrode
Electrochemical

a b s t r a c t
This study presents the degradation of methyl orange in a synthetic solution using an electro-oxidation technique. A novel polymer disk electrode was fabricated in this work using injection molding. Such an electrode is
low cost, mass produced, and efcient to achieve a complete decolorization of methyl orange in the synthetic solution. The performance of the electrode was studied comprehensively. The degradation of methyl orange was
accomplished in only 800 s. at optimum operating conditions of 0.1 M KCl electrolyte solution and constant applied current of 5 mA. The results revealed that the degradation of dye follows an indirect electro oxidation mechanism. It was also found that stirring is a crucial requirement to improve the mass transfer and to enhance the
decolorization rate. The effect of changing the applied current, supporting electrolyte, electrolyte concentration,
and initial dye concentration were also investigated.
2015 Published by Elsevier B.V.

1. Introduction
Degradation of dyes in textile wastewater is a major concern in environmental science. It has been estimated that at least 10% of dyes
used in industries are discharged to the environment [1]. This represents more than 8000 tons of dyes per year that is wasted nowadays
[2]. Textile industries, in particular, release as much as 50% of their processed dyes to the environment [3]. Thus, it is not surprising that removal
of dyes from textile efuents has drawn great attention from many researchers in this eld.
Removal of colors from wastewaters can be achieved using biological, physical, and/or chemical treatment techniques [4]. Both physical
and biological treatment methods are usually environmental friendly
[5]. However, satisfactory results are not always promising, especially
with biological methods where treatment is inefcient for industrial
wastewater containing non-biodegradable dyes [6]. Chemical treatment techniques, on the other hand, can be efcient, but complete degradation is normally costly and sometimes complicated especially when
many chemicals are added [7]. Recently, it was found that combining
more than one treatment technique could lead to reasonable improvement in the treatment efciency and reduction in the process cost [8].
Hybridized treatment methods in the textile industry have been
discussed comprehensively by many authors [911].

Corresponding author.
E-mail address: hayousif@uob.edu.bh (H. Abdulla Yusuf).

http://dx.doi.org/10.1016/j.mee.2015.09.003
0167-9317/ 2015 Published by Elsevier B.V.

Electrochemical treatment, on the other hand, is a single, yet efcient treatment technique. Degradation of dyes electrochemically is
not only safe for the environment, but it also does not involve chemical
reagents in the process [12]. In electrochemical degradation, electrons
act as the reagents that create chemical changes to the dyes. Moreover,
the broken down compounds in the electrochemical degradation process are usually nonhazardous [13] making the process clean and
hence attractive for the treatment of pollutants [14]. Electrochemical
treatment has received great attention due to its efcient applicability
to a wide range of textile water compositions and ow rates, thus, making it a suitable candidate for both micro and macro scale industrial processes [15].
Martnez-Huitle and Brillas [16] reviewed several electrochemical
treatment methods for dye removal in wastewater. Among those, the
electrochemical oxidation technique [17] was one of the most distinctive methods. Removal of azo dyes in particular was achieved using several techniques, some of which were summarized by Singh and Arora
[13]. For example, the UV irradiation technique, in the presence of hydrogen peroxide (H2O2) was investigated for the degradation of methyl
orange [18]. Electrochemical treatment techniques were also reported
extensively for the degradation of methyl orange [7,19]. A wide range
of electrode materials could be used for the electrochemical degradation
of azo dyes in general and methyl orange in particular. Platinum electrodes combined with either microwave activation [20], or a redox mediator [21] showed successful degradation of methyl orange. Dual iron
and graphite anodes in the presence of catalysts [22] have also revealed
promising results where complete decolorization of methyl orange was

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H. Abdulla Yusuf et al. / Microelectronic Engineering 149 (2016) 3136

achieved after 60 min. Kong et al. [12] reported a successful attempt for
the removal of methyl orange in 20 min using electro-oxidation on an
exfoliated graphite electrode. However, to the authors' knowledge,
complete degradation of methyl orange using both a rapid decolorization technique and an inexpensive electrode is limited in the literature.
In this paper, the authors fabricated a novel polymer disk electrode
using an injection molding technique. These electrodes were evaluated
for the treatment of a synthetic solution containing methyl orange as
model. In comparison with previously published studies, these electrodes are low cost, mass produced, and found to be efcient for such
application. The treatment technique involves the electro-oxidation of
KCl solution on the polymer electrode. The utilized technique in this
study is featured by its simplicity and rapidity for dye degradation.
Moreover, the performance of the disk polymer electrode was compared to the commercially available electrodes for the degradation of
methyl orange dye. The effects of changing the operating conditions,
stirring of solution, type and concentration of supporting electrolytes,
applied current, and initial dye concentration were also investigated.

50 bar; injection time 6 s, and cooling time 12 s. The disk electrode

surface was created by an over molding procedure, where clear polystyrene (Northern Industrial Plastics Ltd., Chadderton, UK) ows around
the previously fabricated carbon ber parts. The working electrode was
molded in plates measuring 20 cm 15 cm 0.4 cm; individual plate
electrodes measuring 1 cm 1 cm 0.4 cm were directly cut from
these sheets (Fig. 1a). The diameter of the disk electrode was 2.5 mm.
The surface of the electrode was examined using a scanning electron
microscope (SEM) (EVO LS10, Carl Zeiss NTS GmbH, Germany) with
an EDS energy dispersion X-ray spectrometer (Bruker AXS X Flash
Detector 4010). The SEM image of the disk working electrode surface
is shown in Fig. 1b; close examination clearly shows the carbon bers
(darker areas) and their random dispersion in the polystyrene matrix
(lighter areas).

2. Material and methods

A peak at 0.7 V (oxidation potential) was observed in the presence

of dye solution, but not observed in the absence of the dye solution
(see Fig. 2). This peak is probably attributed to the adsorption of the
dye molecules on the electrode surface and not the direct electrooxidation of the dye. This is because further increase in the dye concentration did not cause any increase in the peak height. The reversible
peaks at approximately + 0.280 V are probably amine peaks as described by Kalyuzhnyi et al. [23] and Zille et al. [24].
In addition, scanning between zero and 1.5 V showed an increase in
the anodic current at higher potential values. This current increased
with increasing electrolyte concentration and scan rate.
It is known that the electrolysis of chlorine solution in an undivided
cell leads to the direct oxidation of chloride ions at the anode to chlorine
(RXN 1) and reduction of water at the cathode to hydroxide ions and
hydrogen gas (RXN 2) [16]. The former explains the rise in the anodic
current at potentials greater than 1 V.

2.1. Chemicals and reagents

Methyl orange dye (MO) (C14H14N3O3SNa; molar mass 327.3 g/mol)
was used as the target organic pollutant. It was purchased from Aldrich
as a powder and used without further purication. Different concentrations of MO dye (13, 20, 30 and 40 ppm) were prepared using deionized
water in 0.1 M KCl (Scharlau Chemie, Spain) solution as an electrolyte
unless otherwise stated.
2.2. Apparatus
Voltammetric measurements were performed using an Autolab
electrochemical system (PSTAT III, Eco Chemie B.V., Utrecht, The
Netherlands) controlled with GPES software (v 4.9) running on a PC. A
conventional three-electrode system was used in a 50 mL standard
glass voltammetric cell (Metrohm, Switzerland). The cell was equipped
with a double junction Ag/AgCl reference electrode and a Pt wire counter electrode both from Metrohm. A disk polymer electrode was used as
the working electrode. A PTFE magnetic stirring bar, agitated by a magnetic stirrer (Corning PC 351), was placed in the bottom of the cell for
stirring the solution during the degradation process. The performance
of the disk electrode was compared to that of conventional 2 mm glassy
carbon, gold, and platinum disk electrodes (Metrohm, Switzerland).
Chronoamperometric/galvanostatic measurement, at different bias
currents, was conducted on 10 ml of different concentrations of MO
solutions, all containing 0.1 M KCl. The extent of color removal was
determined using UV-Vis spectroscopy (path length 1 cm, apparatus:
Shimadzu UV-1800) at its maximum absorption ( = 465 nm). Samples were taken every 200 s, unless otherwise stated. All measurements
were performed at room temperature (normally 21 C).
2.3. Disk electrode fabrication
The working electrode was fabricated in house (School of Chemical
Engineering and Analytical Science, University of Manchester). These
electrodes were injection-molded from a conducting polymer (40%
carbon ber lled-high impact polystyrene (HIPS), RTP 487, RTP Company (UK) Plastics Ltd., Bury, UK). Injection-molded parts were fabricated using a Babyplast 6/6 injection-molding machine (Cronoplast SA,
Barcelona, Spain). Mold tools were fabricated from brass bar stock
using a CAT3D M6 CNC milling machine (Datron Technology Ltd, Milton
Keynes, UK) and conventional tungsten carbide end mills of diameters ranging from 0.15 to 1.0 mm. The molding conditions were as
follows: plasticizing temperature 230 C; injection chamber temperature 220 C; injection nozzle temperature 200 C; injection pressure

3. Experimental results and discussion

3.1. Cyclic voltammetric studies

2Cl Cl2aq 2e

h
i
E0 1:36 vs SHE

2H2 O 2e 2OH H

i
E0 0:83 vs SHE

RXN 1

RXN 2

Moreover, at the pH range studied (pH = 38) the generated chlorine can be hydrolyzed rapidly to generate hypochlorous acid and chloride ions as follows (RXN 3) [16]:

Cl2 H2 OHClO Cl H

h
i
E0 1:49 vs SHE :

RXN 3

Trichloride ion Cl
3 can also be formed but in very low concentrations up to pH ca. 4.0 [16] according to the following reaction:

Cl2aq Cl Cl3 :

RXN 4

The hydrochlorous acid in the solution is in equilibrium with the hypochlorite ion according to the following reaction:

HClOClO H

i
E0 0:89 vs SHE :

RXN 5

Thus, from these CV results, it is suggested that the electrochemical

degradation of the dye in this experiment (high applied potentials) follows the indirect electro-oxidation mechanism [25], which involves the
reaction of the dye molecules with the strong oxidants generated from
the direct anodic oxidation of the chlorine ions present in the electrolyte
[16].

H. Abdulla Yusuf et al. / Microelectronic Engineering 149 (2016) 3136

33

Fig. 1. Injection modeled polymer disk electrode: a) The fabricated design and b) SEM image of the electrode.

3.2. Electrochemical degradation studies

The electrochemical degradation studies on the disk polymer electrode showed an exponential decay in the dye color with time (R2 =
0.9826). Complete decolorization was achieved in only 800 s. The effect
of stirring on the electrochemical degradation process was found to be
signicant in this experiment. Mass transfer is important to the dye degradation since the degradation reaction is highly dependent on the
diffusion rate of the dye in the solution. Thus, the use of stirring has increased the mass transfer of the dye to the electrode surface [26]. This
was evidenced when complete decolorization in the absence of stirring
required twice the time needed when a stirring system was employed.

gold and polymer electrodes respectively. Such comparable performance, even though both electrodes had nearly similar diameters,
could be attributed to the carbon ber microstructure on the electrode
surface [27]. Thus, these results strongly support the suitability of the
polymer electrode for the current study. Quicker degradation was
achieved, as expected, on the platinum electrode [28]. It is reported
that high decolorization efciency can be achieved using the platinum
electrode [16] and was proved in this experiment as less than 3 min
was sufcient for complete degradation of the organic pollutant. However, considering the employed surface area and the total cost of the
electrodes, the advantages of the polymer electrode overweighs that
of the other two electrodes for such application.

3.3. The effect of electrode material

The performance of the disk polymer electrode was compared to
that of glassy carbon, gold, and platinum disk electrodes (Fig. 3). The results revealed close similarities between the polymer electrode and gold
electrode. Complete degradation was achieved in 10 and 13 min on the

Fig. 2. Cyclic voltammograms of 90 ppm methyl orange in 0.1 M KCl solution, at a scan rate
is 0.05 V/s.

Fig. 3. Electrochemical degradation of 13 ppm methyl orange dye using different electrodes. Conditions: Chronopotentiometric/galvanostatic measurement at 5 mA bias current, in 0.1 M KCl electrolyte. Insert is the decolorization rate using the three different
electrodes.

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H. Abdulla Yusuf et al. / Microelectronic Engineering 149 (2016) 3136

Fig. 4. The electrochemical degradation of 13 ppm methyl orange solution at different bias
currents. Inset is the percentage of color removal measured at 1000 s.

3.4. The effect of applied current

Fig. 4 shows the effect of the applied bias current on the methyl
orange color removal. Slower response was observed at lower current values due to the associated reduction in the reaction ux. However, an increase in the applied bias current causes a sharp increase in the
percentage color removal [22,29]. A tenfold increase in the decolorization rate was obtained when the current was increased from 3 mA to
5 mA. However, a plateau was reached at higher current values where
no signicant change in the percentage color removal was observed
(inset of Fig. 4) [25]. The former agrees with Faraday's law that the
amount of electrochemical products is proportional to the current and
is constant at a constant applied current. The plateau at high current
values was attributed to the constant corresponding potential values
for this current range.
Furthermore, the electrical energy consumption for this process was
analyzed at the optimum selected current using the following equation [30]:

Energy consumption



I  V  tf
kW  h

 103
3
Vs
m

where I is the applied bias current (A), V is the corresponding voltage

(V), tf is the time at complete degradation (h), and Vs is the volume of
the solution (m3).
The calculated electrical energy consumption at optimum current of 5 mA was 1.11 kWh/m 3 . This remarkable nding adds a
great value to this work, as there is a signicant saving of energy
[30], which is a major factor affecting the operating cost for such
application.
3.5. The effect of supporting electrolyte
The effect of three supporting electrolytes: KNO3, KCl and Na2SO4,
was studied. The results revealed that total decolorization was obtained
with KCl, whereas very low color removal was obtained with Na2SO4
and no decolorization was achieved with KNO3. A similar observation
has been reported by other researchers [28]. These results suggest
that, in the absence of chloride ions, neither any oxidative species are
produced nor does any direct anodic oxidation of the dye occur [25].
However, with KCl, the decolorization is mainly achieved due to the indirect oxidation with the active chlorine species generated. Although, to
the authors' knowledge, there have been limited reports on the electrochemical degradation of MO on a carbon ber polymer electrode [31],
this work agrees with some studies on the feasibility of the carbon

Fig. 5. The electrochemical degradation of 13 ppm methyl orange solution at different

electrolyte concentrations. Conditions: Chronopotentiometric/galvanostatic measurement at 5 mA bias current. Inset is the effect of KCl concentration on the rate of decolorization. In addition, since further increase in KCl concentration (more than 0.1 M) did not
cause any improvement in the degradation rate, 0.1 M was used as optimal KCl concentration in the successive experiments.

electrodes for the indirect electro degradation of MO with active chlorine [32].
3.6. The effect of electrolyte concentration
Fig. 5 studies the effect of varying the electrolyte concentration on
the methyl orange color removal at constant applied bias current. The
results reveal that there is a linear effect at low electrolyte concentration on the dye color removal up to 0.1 M; however, this effect is not signicant at higher concentrations [22,29]. More than 95% dye color
removal in less than 15 min was achieved in solutions containing a
KCl concentration 0.1 M. The fast color removal rate at higher Cl concentration is attributed to the formation of greater concentration of active chlorine species as illustrated in RXNs 1 and 3 [16] and thus, the
increase in mass transport of the chlorine ions to the polymer electrode
surface [25]. Moreover the inset of Fig. 5 clearly shows that the decolorization rate increases linearly with KCl concentration at low concentrations but was maintained constant at electrolyte concentrations above
0.1 M. However, the increase at lower concentrations was suggested
by Lorimer et al. [28] to the competitions between the chlorine production reaction and the oxygen production reaction. The effect of Cl concentration is signicant not only for its part in the decolorization
reaction but also for increasing the solution conductivity, hence improving the overall efciency of the electrochemical degradation reaction.
Thus, the latter explains the linear characteristic of the decolorization
rate at low concentrations.
3.7. The effect of dye initial concentration
The inuence of the initial dye concentration was studied, for the
concentrations of 13, 20, 30, and 40 ppm, in solutions containing
0.1 M KCl as electrolyte, at a constant applied current of 5 mA. A perfectly t exponential relationship between the initial dye concentration and
the time required for complete color removal was obtained in this experiment. For a given time period, the amount of color removal decreased with increasing initial dye concentration. For example, nearly
100% color removal was achieved in approximately 13 min at the lowest
examined concentration (13 ppm) but only 45% for higher initial concentration. Although, mixing was employed throughout the experiment
and thus the surface area of the electrode was continuously renewed
with the dye molecules, only a certain amount of dye could be degraded.
This is attributed to the limitation imposed by the electrode area and applied current, which limited the electrochemical production of the chlorine active species [25]. From Fig. 6, the time required for complete

H. Abdulla Yusuf et al. / Microelectronic Engineering 149 (2016) 3136

35

With the limit CA = CA0 at t = 0 gives

ln

C A0
kt:
CA
The linear relationship between ln CCA0A and time deduced a pseudo

rst order reaction kinetic, which agrees with the results found in literature [33]. The rate constant value was found to be 4.844 105 h1.
4. Conclusion

Fig. 6. The electrochemical degradation of methyl orange solution at different initial dye
concentrations. Conditions: Chronopotentiometric/galvanostatic measurement at 5 mA
bias current, in 0.1 M KCl concentration. Inset is the effect of dye initial concentration on
the rate of decolorization.

degradation of higher initial dye concentrations can also be estimated

knowing the following relationship:
t 460:11e0:04C 0

where
t
C0

is the time required for complete degradation of dye (s)

is the initial dye concentration (ppm).
Fig. 6 shows the exponential decay in the absorbance value with
respect to time for 20, 30, and 40 ppm initial dye concentrations.
The inset of Fig. 6 depicts that the rate of decolorization decreased
linearly with an increase in the initial dye concentration within the
range examined.

Electrochemical degradation is an environmental friendly technique

for the remediation of wastewater containing azo dyes. This study characterized the use of a novel polymer disk electrode for the degradation
of a synthetic solution containing methyl orange, chosen as a model. In
addition, it showed not only the feasibility of the fabricated polymer
disk electrode for the degradation of MO, but also its competence with
some commercially available electrodes, and those presented previously in the literature. The electrochemical treatment technique was based
on electro-oxidation of KCl solution into chlorine active ions on the
polymer disk electrode followed by their reaction with MO molecules.
The fabricated polymer disk electrode has successfully proved to
achieve a complete degradation of 13 ppm MO solution in only 800 s.,
at the optimum operating conditions. Increasing the initial concentration of MO was found to decrease the decolorization rate exponentially.
A relationship between the initial dye concentration and the percentage
color removal was demonstrated in this study which enables direct estimation of the time required for the degradation of MO at different initial concentrations.
Acknowledgment
The rst author would like to gratefully acknowledge the University
of Bahrain for its nancial and academic support.
References

3.8. Degradation kinetic of methyl orange

The order of the reaction was determined by the integral method
and apparently found to t rst order reaction model for the batch system, with R2 = 0.9743, as shown in Fig. 7, according to the following
equation
r A

dC A
kC A :
dt

Fig. 7. First order reaction kinetic t for the electrochemical degradation of methyl orange
on the disk electrode at optimum condition.

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