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Journal of the Taiwan Institute of Chemical Engineers

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Electrochemical degradation of acid orange II dye using mixed metal

oxide anode: Role of supporting electrolytes
Jingyu Wu a, Zhenzhu He a, Xiaoming Du a, Chunyong Zhang a,b,∗, Degang Fu b,c
a
Department of Chemistry, College of Science, Nanjing Agricultural University, Nanjing, 210095, China
b
Suzhou Key Laboratory of Environment and Biosafety, Suzhou Academy of Southeast University, Dushuhu Lake Higher Education Town, Suzhou, 215123, China
c
State Key Laboratory of Bioelectronics, Southeast University, Nanjing, 210096, China

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

Article history: Here, the electrochemical degradation of 50 mg/dm3 Acid Orange II dye over mixed metal oxide anode has
Received 1 June 2015 been conducted in the presence of different supporting electrolytes (sulfate, chloride, and their mixture of dif-
Revised 10 August 2015
ferent proportion). A factorial design methodology was adopted to evaluate the statistically important input
Accepted 12 August 2015
Available online xxx
variables, among treatment time (30–60 min), flow rate (300–600 ml/min), applied current density (2.58–
5.16 mA/cm2 ) and total concentration of supporting electrolytes (1.0–4.0 mM), on degradation performance;
Keywords: the latter was assessed in terms of color removal rate. The results obtained, demonstrated that the electrolytic
Mixed metal oxide oxidation was strongly favored by the presence of chlorides. In addition, the information obtained from elec-
Boron-doped diamond trochemical measurements and UV–vis spectra were used to better clarify the different roles of operating
Degradation parameters recorded.
Factorial design
© 2015 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Supporting electrolyte

1. Introduction involvement of active chlorine. Most previous studies have shown

More and more researchers have demonstrated that electrochem-
ical oxidation (EO) offers a promising alternative to conventional
wastewater treatment due to its high efficiency and environmental
compatibility [1]. Specifically, the performance of EO is strongly
dependent on the employed anode materials and supporting elec-
trolytes [2]. Research into this area has primarily focused on two
kinds of anode materials (i.e. boron-doped diamond (BDD) and
mixed metal oxide (MMO)), as well as on two kinds of supporting
electrolytes (i.e. Na2 SO4 and NaCl) [3,4]. Compared with BDD, MMO
exhibits lower oxygen over-potential but higher electroactivity
toward the reaction of chlorine evolution. As a result, MMO is found
to be effective in the presence of NaCl whereas BDD yields better
removal in the presence of Na2 SO4 [5,6]. In other words, MMO/Cl–
and BDD/SO4 2– are the most suitable systems for the destruction
of organic pollutants. These results indicate that the interactions
between anode surface and electrolyte salts have a strong impact on
the efficiency of EO.
In recent years, intense research interest has been devoted to in-
vestigating the influence of nature and concentrations of supporting
electrolytes on the performance of EO [7,8]. Among the electrolyte
family, NaCl is regarded as the most fascinating member for the
∗
Corresponding author. Tel.: +86 25 84395207; fax: +86 25 84395207.
E-mail address: zhangchy@njau.edu.cn (C. Zhang).
the superiority of NaCl over other electrolytes in both BDD and MMO
anode cells [9,10]. That is to say, the presence of chloride may exert
strong influences on the reaction kinetics and mechanism for anodic
oxidation processes [11]. However, due to the complex “anode–
electrolyte–solvent” interactions, it is a daunting task to determine
the rules involved in chloride-containing electrolytic systems [5,12].
One solution to this problem is to develop theoretical models to
predict the reaction kinetics and performance, which may facilitate
the optimization of the operating conditions. Several kinetic models,
including those by Comninellis, Polcaro, Rodrigo and Scialdone, were
developed previously [2,5]. As a result, each model has its pros and
cons when used in real applications. Another effective approach is to
employ the design of experiment (DOE) method. It is well accepted
that DOE is capable of revealing quantitatively the relationship
between input and output variables [13,14]. Note that in most pre-
vious studies, the application of classical experimental design (i.e.
one-factor-at-one-time strategy) may result in wrong conclusions
due to the possible interactions between the operating variables [15].
Thus, the employment of suitable DOE method is expected to solve
the problem. However, to our knowledge, statistical investigation re-
garding the role of supporting electrolytes in EO is still quite limited.
Among the DOE, factorial design methodology (FDM) is a powerful
mathematical technique that is worthwhile for modeling, analyzing
and optimizing the influence of operating variables on the responses
[16]. For this reason, we have recently examined the impact of chlo-
rides on the performance of BDD technology using FDM [17]. Some

http://dx.doi.org/10.1016/j.jtice.2015.08.008
1876-1070/© 2015 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Please cite this article as: J. Wu et al., Electrochemical degradation of acid orange II dye using mixed metal oxide anode: Role of supporting
electrolytes, Journal of the Taiwan Institute of Chemical Engineers (2015), http://dx.doi.org/10.1016/j.jtice.2015.08.008
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2 J. Wu et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2015) 1–8

Table 1 workstation (Shanghai, China). The working electrode was a MMO

Independent variables of the 24 factorial design of experiments.
(with effective surface area of 5.0 mm2 ), while a Pt plate and a sat-
Level X1 X2 X3 X4 urated calomel electrode (SCE) were used as counter and reference
TCSE, mM jappl , mA/cm2 Flow rate, ml/min Time, min electrodes, respectively. All measurements were made at 10 ± 1 °C
– 1.0 2.58 300 30
and under nitrogen atmosphere.
+ 4.0 5.16 600 60
2.3. Experimental design and analysis

interesting phenomena, such as the negative effect of salt concentra-
tion and the fluctuating trend of flow rate, were well recorded and in-
terpreted. Regarding the different nature of BDD and MMO, it may be
speculated that a quite different picture will arise when the electrol-
yses are repeated in MMO anode cells. Thus, we have extended our
recent study [17] to exploit the role of chlorides in MMO anode cells.
This study is novel, because it investigates the “anode–electrolyte”
relationship from a statistical point of view. As expected, some new
and important results were obtained and much effort had been made
for their clarifications.
2. Experimental
2.1. Reagents and materials
As mentioned above, the employment of FDM may lead to new
dimension of understanding the role of supporting electrolytes in
EO. Hence, this design had also been employed in the present study.
The adopted input variables and their operating levels were shown
in Table 1, where X1 , X2 , X3 and X4 referred to total concentration
of supporting electrolytes (TCSE, mM), applied current density (jappl ,
mA/cm2 ), flow rate (ml/min) and treatment time (min), respectively.
Specifically, five kinds of salts, listed as 1 100% Na2 SO4 ;  2 75%
Na2 SO4 + 25% NaCl (molar percentage);  3 50% Na2 SO4 + 50% NaCl;
4 25% Na2 SO4 + 75% NaCl and  5 100% NaCl, were tested as sup-
porting electrolytes in the following comparative studies. As a result,
these combinations guaranteed the color removal rate of AO II rang-
ing from 25% to 90% within 60 min of electrolysis. Statistical exami-
nation of the results was performed by a SPSS 17.0 program.

Reagent-grade Acid Orange-II dye (AO II), Na2 SO4 and NaCl were
purchased from Wako (Japan). Deionized water was used for all
stock solutions. Mixed metal oxide (MMO, Ti/(RuO2 )0.65 (IrO2 )0.35 )
and stainless steel (AISI 304) electrodes were provided by Baoji Butai
Corporation (Shanxi, China).
2.2. Degradation experiments and analytical apparatus
The degradation experiments were carried out in a one-
compartment reactor in the batch mode. MMO and stainless steel
plates were used as anode and cathode, respectively. The effective
surface areas of both electrodes were 77.44 cm2 and the electrode
gap was 10 mm. For all entries, the solution volume was 500 ml and
the initial concentration of AO II was 50 mg/dm3 . The solution was
pumped through the MMO anode cell and then returned to reservoir
for recycling. Samples were taken at different time intervals to track
the concentration of AO II, which were done in a Shimadzu UV-1800
spectrophotometer (at wavelength of 482 nm). The TOC concentra-
tion of the reaction medium was determined on a Shimadzu TOC-L
analyzer (the TOC value of 50 mg/dm3 AO II aqueous solution was
21.56 ± 0.08 mg/dm3 ).
Electrochemical measurements were performed in a conven-
tional three-electrode cell powered by a CHI660E electrochemical
3. Results and discussion
3.1. Optimization of various operating parameters
The results obtained in the factorial design for AO II decolorization
on MMO anodes are given in Table 2. The measured output variables
(Y1 to Y5 , in %) are the color removal rate of AO II in the presence of
different supporting electrolytes. (Y1 , Y2 , Y3 , Y4 and Y5 refer to the
case of 1 100% Na2 SO4 ;  2 75% Na2 SO4 + 25% NaCl (molar percent-
age); 3 50% Na2 SO4 + 50% NaCl;  4 25% Na2 SO4 + 75% NaCl;  5 100%
NaCl, respectively).
Statistical analysis of the output variables Y1 to Y5 according to
the methodology of factorial design involves the estimation of the
average effect, as well as the calculation of the main and interaction
effects. The former is the mean value of all response factors, while the
latter are the differences between Z1 and Z2 , where Z1 and Z2 refer to
the average response factors at high and low level respectively of the
input variables and their interactions [18].
The results are shown in Table 3 and Fig. 1, in which PSE (pseudo-
standard error), ME (a margin of error) and SME (a simultaneous mar-
gin of error) are all determined by Lenth’s method [19]. Note that in
the Pareto charts (Fig. 1), only effects greater than the ME decision
threshold, in absolute values, are deemed significant.

Table 2
Design matrix of the 24 factorial experimental design and observed response factors.

Entry X1 X2 X3 X4 Y1 Y2 Y3 Y4 Y5
TCSE jappl Flow rate Time 0% NaCl 25% NaCl 50% NaCl 75% NaCl 100% NaCl

1 – – – – 26.5 25.7 30.9 31.2 29.5

2 + – – – 24.5 25.5 24.5 31.5 46.9
3 – + – – 33.5 34.6 37.4 41.0 44.4
4 + + – – 25.9 28.4 36.4 44.8 54.2
5 – – + – 26.4 33.5 31.6 36.2 42.0
6 + – + – 25.6 27.7 30.2 30.6 57.8
7 – + + – 33.1 38.4 39.6 45.3 51.8
8 + + + – 29.4 34.6 37.9 44.9 65.0
9 – – – + 45.7 45.1 47.1 52.5 50.9
10 + – – + 40.0 44.5 44.3 53.7 70.5
11 – + – + 55.4 55.1 59.8 65.8 62.4
12 + + – + 47.1 45.9 61.5 72.7 77.3
13 – – + + 45.7 56.6 54.4 58.1 58.1
14 + – + + 44.3 47.4 51.6 52.4 64.4
15 – + + + 56.2 61.8 64.1 69.4 74.4
16 + + + + 50.5 56.7 60.7 71.3 88.8

Please cite this article as: J. Wu et al., Electrochemical degradation of acid orange II dye using mixed metal oxide anode: Role of supporting
electrolytes, Journal of the Taiwan Institute of Chemical Engineers (2015), http://dx.doi.org/10.1016/j.jtice.2015.08.008
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ME SME ME SME

a X4
X2
b X4
X3
X1 X2
X1X2 X1
X2X4 X1X2X3
X3 X3X4
X1X3 X1X2
X1X4 X1X4
X1X2X3X4 X1X3
X3X4 X1X2X3X4
X2X3X4 X2X3X4
X2X3 X2X3
X1X3X4 X2X4
X1X2X4 X1X3X4
X1X2X3 X1X2X4
0 5 10 15 20 0 5 10 15 20

Effect Effect
ME SME ME SME
X4
c X4
X2
d X2
X3 X3
X1 X2X4
X2X4 X1X2X4
X2X3 X1
X1X2X3 X1X3X4
X1X3X4 X1X2X3X4
X1X2 X1X2
X2X3X4 X1X3
X3X4 X1X2X3
X1X4 X1X4
X1X2X4 X2X3X4
X1X3 X3X4
X1X2X3X4 X2X3
0 5 10 15 20 0 5 10 15 20 25

Effect Effect

ME SME
X4
e X1
X2
X2X3X4
X3
X1X3
X1X2X3X4
X1X4
X1X2
X1X2X4
X1X3X4
X3X4
X2X3
X1X2X3
X2X4
0 5 10 15 20

Effect
Fig. 1. Pareto charts of the effects for color removal for the full 24 factorial design. (Supporting electrolytes: a: 100% Na2 SO4 ; b: 75% Na2 SO4 + 25% NaCl; c: 50% Na2 SO4 + 50% NaCl;
d: 25% Na2 SO4 + 75% NaCl; e: 100% NaCl). Common bars: positive effects; Bars with arrows: negative effects.

Please cite this article as: J. Wu et al., Electrochemical degradation of acid orange II dye using mixed metal oxide anode: Role of supporting
electrolytes, Journal of the Taiwan Institute of Chemical Engineers (2015), http://dx.doi.org/10.1016/j.jtice.2015.08.008
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Table 3 to make a short summarization of the previous results obtained in

Average and main effects of the independent variables and their two and higher order
BDD anode cells [17]. Briefly, the most important points include: (i)
interactions of the 24 factorial design on the response factors Y1 to Y5.
the order of significance is: reaction time > flow rate > jappl > TCSE;
Effect Y1 Y2 Y3 Y4 Y5 (ii) the significance of reaction time remains almost unchanged for
(0% NaCl) (25% NaCl) (50% NaCl) (75% NaCl) (100% NaCl)
all electrolytes media; (iii) the effect of flow rate shows fluctuating
Average 38.11 41.35 44.50 50.09 59.90 trend with changing chloride proportion; and (iv) the effect of TCSE
Lenth’s PSE 0.83 0.89 1.70 2.02 1.83 is negative for most cases, and it turns positive but insignificant when
ME 1.79 1.92 3.67 4.30 3.95 100% NaCl is employed.
SME 3.52 3.77 7.21 8.71 7.76
Some phenomena may thus be observed from the inspection of
Fig. 2.
25
(1) Along with experimental parameters, the reaction time is of
greatest importance for the electrochemical oxidation of AO II
20 dye. However, the effects of this parameter fade away for full
X4: reaction time chloride media;
(2) The importance of jappl and flow rate in MMO anode cells are
15 X2: applied current density quite different from those recorded in BDD anode cells. Specif-
ically, flow rate exhibits weak effects for all entries;
10 (3) For most cases, the influence of TCSE is negative, but it shows
Effect

a sudden rise or a jump for chloride media.

5 3.2. Interpretation of the experimental results

X3: flow rate To interpret the results, please first, consider the following points:
0
(1) Electrochemical oxidation may occur via direct pathways (direct
electron transfer on the anode) and indirect pathways (electro-
-5 X1: electrolyte concentration
generated oxidizing species, e.g., H2 O2 , Cl2 and O3 ) [1]. The former
possesses slow kinetics while the latter is more efficient due to
0 20 40 60 80 100
the strong power of electrogenerated oxidants. As previously
Percentage of NaCl in the employed electrolytes, % indicated, the contribution of direct oxidation is almost negligible
for MMO anode cells [4,8,21];
Fig. 2. The values of the main effects versus percentage of NaCl in the employed elec-
trolytes. (2) In the presence of sulfate, the reactions occur heterogeneously
considering that AO II molecules must be transported to the an-
ode surface first, and then be oxidized there. But in the presence
Based on the above, the models describing the relationship be- of chloride, the reactions mainly occur homogeneously in the bulk
tween input and output variables are constructed as follows (Eqs. (1)– solution [22];
(5)). Note that non-significant effects have been excluded according (3) The active electrode (e.g., IrO2 - and RuO2 -based MMO) favors the
to Lenth’s method. interaction with hydroxyl radicals (•OH), resulting in the trans-
Y1 = 38.11 − (4.40/2)X1 + (6.55/2)X2 + (20.00/2)X4 formation into a higher oxide surface (MOx+ 1 ). However, the oxi-
dation power of MOx+ 1 is much lower than that of the quasi free
− (1.93/2)X1 · X2 + (1.83/2)X2 · X4 (1) •OH on BDD surface [23];

(4) Compared with BDD anode, electrochemical oxidation by MMO

Y2 = 41.35 − (5.01/2)X1 + (6.19/2)X2 + (6.49/2)X3
+ (20.59/2)X4 + (2.59/2)X1 · X2 · X3
Y3 = 44.50 + (10.35/2)X2 + (21.88/2)X4
Y4 = 50.09 + (12.65/2)X2 + (23.41/2)X4
Y5 = 59.90 + (16.43/2)X1 + (14.78/2)X2 + (4.25/2)X3
+ (18.00/2)X4 − (4.00/2)X1 · X2 + (5.95/2)X2 · X3 · X4
where Yi is the decolorization rate (%) in the presence of different
supporting electrolytes, Xi are the transformed forms of the input
variables. In addition, the accuracy of the above models may be con-
firmed by the residuals test as reported elsewhere [20] (data not
shown).
The above results clearly demonstrate the differing impacts of the
operating variables with respect to the nature of supporting elec-
trolytes. Specifically, Fig. 1 reveals that among the interactions, only
a few two-factor and three-factor interactions are significant. Thus,
only the case of the main effects is concerned in the following. For
comparison purposes, the main effects of the four input variables, as
a function of the electrolyte composition, are plotted in Fig. 2. Be-
sides, to gain a better understanding on the results, we would like
anode has a greater influence by the presence of Cl− , due to their
(2) inefficiency to produce •OH [24,25];
Based on the above analyses, the effects of four input variables are
(3) discussed as follows:
(1) Effect of total concentration of supporting electrolytes (X1 ). As
shown in Fig. 2, the removal efficiency of AO II on MMO anode de-
(4) creases with rising sulfate concentration (for sulfate media), show-
ing similar trend in correlation with that obtained in BDD anode cells
[17]. Furthermore, the impact of this parameter increases slowly with
rising chloride proportion, and it becomes positive when the molar
(5)
percentage of NaCl exceeds 70%. This outcome confirms that the ef-
ficiency of treatment is strongly inhibited by the presence of SO4 2− ,
which may be explained by the lack of participation of •OH in AO II
degradation when MMO is employed. Another possible explanation
may be the blocking effect as discussed in our previous report (i.e. the
active sites of the anode surface may be blocked by sulfate ions) [17].
However, the situation becomes interesting when 100% NaCl are
employed. Our results clearly indicate a sudden rise or a jump in the
significance of TCSE for chloride media. Please consider, once the in-
hibiting effect of SO4 2− is removed, the adsorption of Cl− at MMO
surface will greatly promote the formation of active chlorine, thus re-
sulting in enhanced treatment performance.
Here, it is to be noted that some complex situations will arise
when extending the window of electrolyte concentration, for it

Please cite this article as: J. Wu et al., Electrochemical degradation of acid orange II dye using mixed metal oxide anode: Role of supporting
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a 1200
Electrolytes:
1.0 mM
b 800 Electrolytes:
1000 25% NaCl + 75% Na2SO4 50% NaCl + 50% Na2SO4 4.0 mM
600

-2
800
1.0 mM
-2

(IT - IB), 10 mA cm
(IT - IB), 10 mA cm

600 400

-3
400
-3

4.0 mM 200
200

0
0

-200 -200

-400
-400
0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0

E, V vs SCE E, V vs SCE

c 1000
900 Electrolytes: 4.0 mM d 1600
Electrolyte:
1400 4.0 mM
800 75% NaCl + 25% Na2SO4 100% NaCl
1200
-2

700
mA cm

-2
mA cm

600 1000
500
1.0 mM
800
1.0 mM
-3

400
(IT - IB), 10

600
-3
(IT - IB), 10

300
400
200
100 200

0 0
-100
-200
-200
-400
-300
-600
0.0 0.5 1.0 1.5 2.0 2.5 3.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
E, V vs SCE E, V vs SCE
Fig. 3. Comparison of voltammetric currents associated with the evolution of active chlorine on MMO anode in the presence of different supporting electrolytes (base electrolyte:
0.2 M KH2 PO4 , scan rate: 50 mV/s).

60 90
a Supporting electrolytes: b Supporting electrolytes:
75% Na2SO4 + 25% NaCl 80 100% NaCl
50
70 color
color TOC
40 TOC 60
Removal rate, %
Removal rate, %

50
30
40

20 30

20
10
10

0 0
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time, min Time, min
Fig. 4. Comparison of TOC and color removal efficiency. (50 mg/dm3 AO II, TCSE of 4.0 mM, flow rate of 600 ml/min and jappl of 5.16 mA/cm2 ).

Please cite this article as: J. Wu et al., Electrochemical degradation of acid orange II dye using mixed metal oxide anode: Role of supporting
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4 4
a Electrolytes:25%NaCl+75%Na2SO4
TCSE:1.0mM
b Electrolytes:100%NaCl
TCSE:1.0mM
jappl:2.58mAcm-2 jappl:2.58mAcm-2
3 2.815 3 2.755
0min
Absorbance,au

Absorbance,au
0min

1.871 60min
2 2 1.740 60min
1.222
1.153
1 1

0 0

200 300 400 500 600 700 200 300 400 500 600 700
Wavelength,nm Wavelength,nm

4 4
c Electrolytes:25%NaCl+75%Na2SO4
TCSE:4.0mM d Electrolytes:100%NaCl
TCSE:4.0mM
jappl:2.58mAcm-2 jappl:2.58mAcm-2
3
2.808 3 2.750
0min 0min
Absorbance,au

Absorbance,au
2.031
2 60min 2 60min
1.477 1.595

0.980
1 1

0 0

200 300 400 500 600 700 200 300 400 500 600 700
Wavelength,nm Wavelength,nm

4 4
e Electrolytes:25%NaCl+75%Na2SO4
TCSE:1.0mM f Electrolytes:100%NaCl
TCSE:1.0mM
jappl:5.16mAcm-2 jappl:5.16mAcm-2
3 2.815 3
0min 2.755
0min
Absorbance,au

Absorbance,au

2
1.738 60min 2 60min
1.326
1.079
1 1 0.705

0 0

200 300 400 500 600 700 200 300 400 500 600 700
Wavelength,nm Wavelength,nm
4 4
g Electrolytes:25%NaCl+75%Na2SO4
TCSE:4.0mM
h Electrolytes:100%NaCl
TCSE:4.0mM
jappl:5.16mAcm-2 jappl:5.16mAcm-2
3 2.808 3 2.750
0min
0min
Absorbance,au
Absorbance,au

1.836 60min 2
2 60min

1.215
0.963
1 1

0.309

0 0

200 300 400 500 600 700 200 300 400 500 600 700
Wavelength,nm Wavelength,nm

Fig. 5. Temporal absorbance variation of UV–vis of AO II during anodic oxidation on MMO electrode under different operative conditions (TCSE: total concentration of supporting
electrolytes; flow rate: 600 ml/min).

Please cite this article as: J. Wu et al., Electrochemical degradation of acid orange II dye using mixed metal oxide anode: Role of supporting
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is necessary to take into account many influencing factors which
may be ignored in the lower ones. These factors include the S2 O8 2−
formation reactions in sulfate media, the competitive reactions
between active chlorine and hydroxyl radicals, and the formation
and accumulation of chlorinated organic intermediates, which are
inherently of great complexity than the mass-transport theory (e.g.,
the Comninellis model) [1].
(2) Effect of applied current density (X2 ) and flow rate (X3 ). The jappl
is an important parameter in EO for it affects the electrolysis kinet-
ics and process economics, while flow rate is directly linked to the
hydrodynamic conditions of the system [1]. Analysis of Fig. 2 shows
that the effect of jappl is more significant compared with that of flow
rate. As mentioned above, direct electrochemical oxidation is almost
negligible for active MMO anodes (i.e. RuO2 and IrO2 ). Following this
analysis, indirect oxidation mediated by higher oxide (MOx+ 1 ) and
active chlorine should be the dominant reaction in the system. Ac-
cording to the theoretical model developed by Scialdone et al., the
synergy of a low flow rate and a high jappl is expected to give a supe-
rior oxidation rate for active MMO anode [5]. While for BDD anode,
the desired operating conditions are a high flow rate and a low jappl .
This is not surprising since the oxidation via •OH is strongly affected
by mass transfer rate on the BDD surface. As a result, a comparison
between the results obtained in these two anode cells well confirms
the accuracy of the Scialdone model.
(3) Effect of reaction time (X4 ). Clearly the effect of this parameter
is very similar to that obtained in the case of BDD anode, and the only
difference lies in the decrease of importance in chloride media (100%
NaCl). The reason of this behavior may be explained by the high ox-
idation rate of chlorine-mediated homogeneous reaction, as well as
by the increased competitive consumption of oxidants through par-
allel reactions with intermediates [24]. In other words, the reaction
intermediates may be directly involved in the anodic oxidations that
cause active chlorine depletion, thus resulting in decreased degrada-
tion efficiency.
3.3. Comparison of voltammetry curves and UV–vis spectra
In this section, we will firstly present some critical evidences
on the impact of supporting electrolytes by means of electrochem-
ical measurements. A previous literature reveals that linear sweep
voltammetry (LSV) may be used to measure the efficiency toward the
evolution of active chlorine on various anode materials [22]. Consid-
ering that the main reactions on MMO surface are occurring through
active chlorine pathways, the information from such measurements
can help to explain some experimental results. Specifically, the ca-
pability of chlorine evolution is evaluated by the current difference
(IT –IB ) magnitude, where IT and IB refer to the total current densities
recorded in the presence and in the absence of chlorides, respectively.
As can been seen from Fig. 3, the (IT –IB ) magnitude recorded well
illustrates the roles of TCSE in the presence of different electrolyte
salts. Briefly, depending on the employed chloride proportion, TCSE
demonstrates three different effects toward chlorine evolution: neg-
ative (Fig. 3a), inapparent (Fig. 3b and c) and positive (Fig. 3d). Clearly,
these effects agree well with the trends of TCSE shown in Fig. 2. In ad-
dition, the negative magnitude recorded in the low potential region
(E < 1.2 V versus SCE) is indicative of the occurrence of adsorption
phenomenon on MMO anode.
Next, it should be noted that absorbance is used here to indicate
the progress of the oxidation process. As is known, information about
the reactivity of the chromophore groups (–N=N–) contained in the
AO II molecule may be inferred from absorbance measurements, but
not necessarily about the organics concentration [4,26]. Alternatively,
the actual mineralization of the dye molecule can be evaluated by
TOC measurements, which is the most essential parameter to indicate
whether the complete removal of organics is attained or not. Besides,
it may be assumed that there exists a relation between decolorization
Please cite this article as: J. Wu et al., Electrochemical degradation of acid orange II dye using mixed metal oxide anode: Role of supporting
electrolytes, Journal of the Taiwan Institute of Chemical Engineers (2015), http://dx.doi.org/10.1016/j.jtice.2015.08.008
[m5G;August 27, 2015;21:6]
7
rate and mineralization rate. To confirm the hypothesis, two repre-
sentative entries were chosen for further investigation. As shown in
Fig. 4, for both cases, higher decolorization rate means higher min-
eralization rate. This is an important observation, because it demon-
strates that active chlorine species may also promote the mineraliza-
tion of the dye molecules. In other words, efficient degradation of AO
II and its aromatic intermediates may also be achieved in the pres-
ence of chlorides. Please consider that, the chloride concentrations
employed here (< 4.0 mM) are rather low, thereby suppressing the
formation of recalcitrant chlorinated organic intermediates. The simi-
lar and differing impact of sulfate and chloride electrolyte will also be
appreciated in the spectra from the following measurements (please
refer to Fig. 5).
Last, the presentation of typical UV–vis spectra allows us to
harvest additional information about the effect of variables in the
electro-oxidation processes of AO II (Fig. 5). Specifically, the values
of the absorbance measured at wavelength of 482 nm (λmax ) are also
presented to better identify the degradation efficiency. As a result,
one may “see” the role of operating parameters directly by making
comparisons between the chosen figures. Several conclusions may
thus be drawn from the comparisons.
(1) The process with chloride media is more efficient than that with
chloride/sulfate media (please refer to the variation of the transi-
tions at 311 nm and 482 nm, as well as their shoulder at 350 nm);
(2) The addition of electrolyte salt to the original dye solution leads
to a small decrease in the measured absorbance (at 482 nm), indi-
cating the complex interaction between electrolyte salts and dye
molecules [12];
(3) An important observation is that effect of TCSE (X1 ) is negative for
sulfate/chloride media but positive for chloride media, which is
consistent with the sign of coefficients in Eqs. (2) and (5);
(4) Another important observation is that the influence of jappl in
MMO anode cells is more significant than that in BDD anode cells;
(5) The last observation from Fig. 5b, d, f and h is that for chloride me-
dia, the color removal rate increases rapidly for the first 30 min,
whereupon it undergoes a much slower rise. This outcome may be
attributed to the high oxidation power of active chlorine, as well
as to the formation and accumulation of the aromatic reaction in-
termediates (which may compete with their parent compound for
oxidants).
As a result, the above features are in perfect accordance with the
role of input variables recorded in Section 3.1.
4. Conclusions
This research investigated the role of supporting electrolytes in
MMO anode cells. To evaluate in a coherent way the significance of
the input variables involved, a factorial design methodology was fol-
lowed. It was made clear that sulfates exhibited significant inhibiting
effect on the treatment performance, whereas chlorides exhibited the
contrary effect. Furthermore, a comparison between the results ob-
tained in MMO and BDD anode cell revealed that the importance of
jappl and flow rate varied with respect to the nature of anode materi-
als. As a result, the efficiency of anodic oxidations was strongly linked
to the current-anode–electrolyte-flow rate interaction. Once this in-
teraction is better understood, it will greatly promote the research
regarding the real application of EO technology. Presently, studies are
underway to assess the relationship between these four variables.
Acknowledgments
This study has received funding from the Fundamental Research
Fund for the Central Universities, Nanjing Agricultural University un-
der the grant agreement No. KYZ201219.
JID: JTICE
ARTICLE IN PRESS [m5G;August 27, 2015;21:6]

8 J. Wu et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2015) 1–8

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Please cite this article as: J. Wu et al., Electrochemical degradation of acid orange II dye using mixed metal oxide anode: Role of supporting
electrolytes, Journal of the Taiwan Institute of Chemical Engineers (2015), http://dx.doi.org/10.1016/j.jtice.2015.08.008