Journal of New Materials for Electrochemical Systems 5, 315-321 (2002)

c J. New. Mat. Electrochem. Systems

Photoelectrochemical Degradation of Orange II Textile Dye on Nanostructured WO3 Film

Electrodes

Jin Luo, Jeremiah Yartym and Maria Hepel

Department of Chemistry, State University of New York at Potsdam,
Potsdam, New York 13676, USA
( Received August 30, 2001 ; received in revised form December 19, 2001 )
Abstract: Interfacial photodecomposition of organic compounds has been investigated using transition metal oxide semiconductor electrodes in
aqueous solutions. It has been found that the textile azo dyes, which are ubiquitous pollutants in industrial waste waters, can be decomposed using
electrochemical photolysis scheme. We report here on an efficient photodegradation of Orange II azo dye on a WO3 nanocrystalline film electrode.
The degradation process is fast and can be completed in a few minutes of the reaction time, under optimum conditions. The reaction progress was
monitored by recording solution absorbance decay at the Orange II absorbance maximum at = 486 nm. The reaction rate was found to depend
linearly on the irradiation intensity and concentration of Cl ions. The reaction order with respect to Orange II dye is 1, up to the concentration of
ca. 0.12 mM. The intermediates formed during the photoelectrochemical degradation of Orange II were detected by means of a high-performance
liquid chromatography. The possible dye degradation mechanism is proposed.
Key words : Tungsten trioxiole; nanostructured film; Orange II dye; phoyoelectrochemical degradation

1.

INTRODUCTION

photocatalytic degradation [13-28]. The light and thermal processes were found to be effective factors in Orange II dye degradation [13]. The degradation rates of Orange II dye are influenced by the solution pH [14-16, 29, 31]. The presence of H2 O2
tends to accelerate photocatalytic degradation of Orange II dye
[14, 16-21]. The intermediate species in the process of Orange
II dye photodegradation, such as H2 O2 and hydroperoxy radical
HO2 , were reported [15, 22, 23]. Previous studies on photochemical degradation of Orange II were mainly carried out on
colloidal suspensions of TiO2 semiconductor nanoparticles [15,
20, 23-25]. A disadvantage of this approach is the need of the
separation of suspended semiconductor particles and the treated
solution. The problem is not an issue in photoelectrochemical
systems.

Recently a significant number of papers has been published

[1-28] devoted to the photocatalytic degradation of organic pollutants. TiO2 semiconductor nanoparticles and some composite
semiconductors are regarded as good carriers for a photocatalytic degradation because they are highly photoreactive, inexpensive, non-toxic, chemically and biologically inert. The semiconductor photocatalysts must be photostable and have suitable
bandgaps. The TiO2 aerogels for efficient photocatalytic decomposition of organic molecules were reported by Tomkiewicz
et al. [6,7].
Orange II, a textile azo dye, has a high photo- and thermalstability. Degradation of Orange II dye has been widely studied
[13-32]. Orange II can be oxidized on Fe, Ti, and Al oxides
[29-32]. Most degradation studies were carried out through a

Photoelectrochemical degradation is an efficient method of degrading organic dyes [33]. The efficiency of the photoelectrochemical degradation process depends not only on the selection
of a suitable supporting electrolyte and pH values, but also on

To whom correspondence should be addressed:

Email: hepelmr@potsdam.edu

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Jin Luo et al./ J. New Mat. Electrochem. Systems 5, 315-321 (2002)

the electrode potential and preparation conditions of the semiconductors involved.

wire was used as the counter electrode. All the potentials are
quoted with respect to the saturated calomel electrode (SCE).

TiO2 and WO3 semiconductor nanoparticles can serve as carriers for photocatalytic degradation of Orange II and other dyes.
Tungsten trioxide is an important photoelectrochemical material
especially in electrochromic applications and has been studied
extensively in this laboratory [33-37, 39]. WO3 film can also
be used as a photoanode for visible-light assisted photoelectrochemical degradation of organic pollutants [33, 38, 39]. In general, WO3 has a slightly narrower bandgap and more positive
valence band edge than TiO2 . Thus, the photogenerated holes
have a greater ability to oxidize organic pollutants in the solution. Our previous results [33] showed that the photoelectrochemical degradation rates of Naphthol Blue Black dye on WO3
film electrodes were higher than those on TiO2 semiconductor
nanoparticulate film electrodes. The WO3 nanocrystalline film
electrodes, prepared by electrodeposition [37], were selected
as photoelectrodes for the photoelectrochemical degradation of
Orange II dye in this paper.

2.3

2.
2.1

EXPERIMENTAL
Chemicals

Tungsten powder (Alfa, APS 1-5 micron, 99.9%) was obtained

from Johnson Matthey Company. Orange II dye was obtained
from the Aldrich Chemical company. The formula of Orange II
dye is shown as follows. Other reagents used in the experiments
were of analytical reagent quality.

Preparation of WO3 nanocrystalline films

Solutions for the electrodeposition of WO3 films were prepared

by dissolving 2 g of tungsten powder in 10 mL of aqueous 30%
hydrogen peroxide solution. After the exothermic reaction had
ended, 100 mL of MilliQ water and 30 mL of 2-propanol were
added.
The cleaned Pt gauze electrodes ( A = 66.1 cm2 ) were immersed
in the electrodeposition solution and biased at -450 mV for 60
minutes. The obtained WO3 films were carefully washed with
MilliQ water and ethanol, and then annealed at 400 C.
As shown in our previous paper [37], the electrodeposited WO3
was composed of nanocrystallites with an average size of
20-40 nm and the electron diffraction data revealed the hexagonal unit symmetry of the deposited films. The amount of a
semiconductor coated on a Pt gauze substrate was determined
by weighing. Typically, the mass of a WO3 film coated on a Pt
substrate was ca. 3.3 mg.
2.4

Procedures

The concentration of Orange II dye in the solution was determined by measuring the absorbance of the dye solution using
a HP 8452A Diode Array UV-Vis Spectrophotometer. The extinction coefficient, at = 486 nm was found to be  = 2.044
104 M1 .
A High-Performance Liquid Chromatograph (HP 1050 HPLC)
was used for chromatographic analysis. The separation column
was Zorbax SB-C18 (10 m, 4.6 mm 25 cm) and the buffers
were 0.5 % ammonium acetate + 2 % acetic acid diluted by
15 % acetonitrile + 85 % water and acetonitrile.
The photoelectrochemical experiments were performed at room
temperature (~20 C).
3.

2.2

RESULTS AND DISCUSSION

Apparatus

A standard photoelectrochemical setup was employed for photoelectrochemical degradation experiments. It was composed of a microcomputer controlled potentiostat (Model PS-1705,
ELCHEMA) and a 500 W Quartz Halogen Lamp as the illumination source. The irradiation intensity was detected using a
Radiation Meter (Model 30A-P, Optronics Ltd.). The average irradiation intensity at the surface of the semiconductor electrode
was 0.35 W/cm2 . All experiments were performed in threeelectrode electrochemical cells. A cell with quartz window was
used for dye degradation experiments. Semiconductor film electrodes were used as the working electrodes. A saturated calomel
electrode (SCE) was used as the reference electrode and a Pt

The absorption spectrum of Orange II in different supporting

electrolytes, 0.5 M NaCl, 0.5 M Na2 SO4 , 0.5 M NaClO4 and
0.5 M NaNO3 , show a major absorption maximum at
= 486 nm, corresponding to the ground state absorption of Orange II molecule. The calibration experiments indicate that the
absorbance at 486 nm is proportional to the concentration of
Orange II dye for concentrations up to 1104 M.
The photoelectrochemical degradation experiments were carried out in different supporting electrolytes containing Orange II
dye, such as NaCl, NaNO3 , NaClO4 , and Na2 SO4 . The absorbance spectra, obtained after degradation time = 30 min,
are presented in Figure 1. We have found that the degrada-

Photoelectrochemical Degradation of Orange II Textile Dye. / J. New Mat. Electrochem. Systems 5, 315-321 (2002)

317

tion rates were the highest in NaCl solutions. To obtain optimum photoelectrochemical degradation conditions on the WO3
nanocrystalline film electrodes, the effects of various parameters were tested and they are discussed below.

Figure 1: UV-Visible absorption spectra of 8105 M solutions of Orange II dye after 30 min. of photoelectrochemical
degradation on a WO3 film electrode in different supporting
electrolytes: (1) 0.5 M NaCl, (2) 0.5 M Na2 SO4 , (3) 0.5 M
NaClO4 , (4) 0.5 M NaNO3 .

3.1

Effect of Cl ion concentration on Orange II dye degradation rate

To understand the effect of Cl ion concentration, the photoelectrochemical degradation experiments were carried out in
Orange II dye solutions with different concentration of NaCl
supporting electrolyte. The spectra of dye solution after photoelectrochemical degradation are shown in Fig. 2. The concentration of Orange II dye was monitored by measuring absorbance of the dye solution at = 486 nm. As shown in
Fig. 2, the remaining dye concentration at the end of the degradation experiments decreases with increasing NaCl concentration. This suggests that the oxidation products of Cl ions act
as promoters of the Orange II dye degradation reaction. The Orange II dye is fully degraded in 0.5 M NaCl after 30 minutes. To
investigate the photoelectrochemical degradation of Orange II
dye, 0.5 M NaCl was selected as the supporting electrolyte in
following experiments.
3.2 Effect of electrode potential
As indicated in earlier works on photoelectrochemical decomposition of azo compounds [33], the dye decomposition rate
is very sensitive to changes in the electrode potential. To select the optimum potential, the photoelectrochemical degradation experiments of Orange II dye were performed at different
electrode potentials. The Orange II dye concentration decay
was followed by the absorbance decay at = 486 nm. The obtained absorbance transients are presented in Fig. 3a and the
initial degradation rate as a function of the electrode potential
is presented in Fig. 3b. The whole spectra of dye solutions

Figure 2: UV-Visible absorption spectra of Orange II dye solutions after photoelectrochemical degradation on a WO3 film
electrode at E = 1.08 V vs. SCE and for a degradation time
= 30 min. Solutions: 8105 M Orange II dye with different
concentrations of NaCl, C [M]: (1) 0.1, (2) 0.3, (3) 0.5, (4) 0.7,
(5) 1.0.

after photoelectrochemical degradation are shown in Fig. 4.

As seen in Fig. 3, the general trend is that the initial degradation rate increases with increasing electrode potential. The dye
degradation rates increase remarkably at potentials over 1.00 V.
When the electrode potential is increased above 1.20 V, the polarization currents increase sharply. In this case, the decomposition of Orange II dye is associated mainly with electrogenerated holes supplied under the high external electric field,
rather than photogenerated holes. Though the dye degradation rate is faster at higher potentials, the polarization current
is also larger and the consumption of electrical energy is higher.
In this potential range, Faradaic efficiency of the dye degradation process decreases with increasing potential. The optimum
Faradaic efficiency and reaction rate are found in the potential
range from E = 1.08 to E = 1.12 V in 0.5 M NaCl supporting
electrolyte. The effect of electrode potential is consistent with
the dye degradation arising mainly from photo-generated holes
rather than from a photosensitization on the semiconductor surface, found also for TiO2 nano-particulate films [5].
The photoelectrochemical degradation rate on the annealed WO3
film electrode is higher than that on the unannealed WO3 film
electrode. There was only a slight decrease in the degradation
rates when the annealed WO3 film was reused. It is advantageous that the annealed WO3 films can be used repeatedly as
it lowers the cost of the photoelectrochemical degradation process.
The photoelectrochemical degradation rate of Orange II dye increases with decreasing pH, with optimum range from pH 1.0
to pH 4.5.

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Jin Luo et al./ J. New Mat. Electrochem. Systems 5, 315-321 (2002)

3.3

Evaluation of the rate constant for photoelectrochemical degradation of Orange II dye

The effect of initial concentration C0 of Orange II dye on the

degradation rate in NaCl supporting electrolyte was investigated
under illumination with 500 W quartz halogen lamp, for
solutions with dye concentration ranging from 1105 to
1.2104 M. The absorbance transients recorded for Orange II
dye during the photodegradation experiments are shown in Fig.
5, for different initial concentrations of Orange II, in 0.5 M NaCl
supporting electrolyte. The degradation rate constant can be determined assuming that the Langmuir-Hinshelwood mechanism
is operating here, similar to other dye degradation processes on
semiconductor surfaces, which were evaluated by Turchi and
Ollis [40]. A generalized formula describing this type of mechanism is represented by the equation:

r=

Figure 3: A) Decay of the Orange II dye absorbance ( = 486

nm) with time during its photoelectrochemical degradation on a
WO3 film electrode in 0.5 M NaCl solutions containing 8105
M of Orange II dye at different potentials E [V vs. SCE]: (1)
0.90, (2) 1.00, (3) 1.05, (4) 1.08, (5) 1.10, (6) 1.12. B) Dependence of the initial dye degradation rate on bias potential for a
WO3 film electrode in 0.5 M NaCl + 8105 M Orange II dye.

k 0 KCo
1 + KCo

(1)

where k is the reaction rate constant and K is the adsorption

equilibrium constant. By plotting the initial reciprocal reaction rate, 1/r0 , versus the initial reciprocal dye concentration,
1/Co , the values of constants in equation (1) can be determined.
The experimental data for degradation of Orange II dye represent a linear relationship, 1/r0 vs. 1/Co , as illustrated in Figure 6. From the slope and intercept of the linear least-square fitting line to the experimental data, we have determined value of
kK = 2.59 105 cm2 sec1 , k = 2.9109 M cm2 s1 ,
and K = 8.3103 M1 , at E = 1.08 V in 0.5 M NaCl supporting
electrolyte and under illumination with 500 W quartz halogen
lamp. These experimental data indicate a weak adsorbability
of the dye. The degradation process is of the first-order with
respect to the Orange II dye in a concentration range up to ca
1.2104 M.
3.4

Analysis of intermediates and final products

using HPLC

In order to identify the intermediates and final products of

the photoelectrochemical degradation of Orange II dye, as
well as to probe the degradation mechanism of the dye, a
high-performance liquid chromatography (HPLC) was employed.

Figure 4: UV-Visible absorption spectra of Orange II dye solutions after photoelectrochemical degradation on a WO3 film
electrode, at different potentials E [V vs. SCE]: (1) 0.90, (2)
1.00, (3) 1.05, (4) 1.08, (5) 1.10, (6) 1.12. Degradation time:
= 30 min, solutions: 0.5 M NaCl + 8105 M Orange II dye.

Fig. 7 presents the HPLC separations obtained for dye solution

samples taken during photoelectrochemical degradation experiments. It can be seen that the main peak at the retention time
tR = 16.5 minutes, due to Orange II dye, decreases gradually
and disappears after the degradation time = 180 min. There
are several separation peaks appearing during the degradation
experiment, which can be ascribed to the intermediates of the
Orange II dye degradation. They are most likely naphthol and
para-phenol derivatives. The intermediate at tR = 12 s has still

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to be identified. Further investigations of end products of Orange II dye degradation are underway in this laboratory.

Figure 5: Decay of the Orange II dye absorbance ( = 486

nm) with time during its photoelectrochemical degradation on
a WO3 nanocrystalline film electrode, at 1.08 V vs. SCE, in
0.5 M NaCl supporting electrolyte containing different initial
concentration of Orange II dye, Co [M]: (1) 1.2104 , (2)
1.0104 , (3) 8105 , (4) 6105 , (5) 4105 , (6) 2105 ,
(7) 1105 .

Figure 7: High-performance liquid chromatograms of Orange

II dye solution during photoelectrochemical degradation. Initial
dye solution: 8105 M Orange II dye + 0.5 M NaCl, degradation time [min]: (1) 0, (2) 5, (3) 10, (4) 20, (5) 30, (6) 180.
3.5

Orange II Dye degradation mechanism

Photoelectrochemical degradation process on a semiconductor

nano-particulate film electrode can be described as follows. Semiconductor particles in the film generate electron-hole pairs under the illumination with UV-visible light. Under the influence
of applied electric field, the photogenerated holes in the valence band of the semiconductor nano-particles traverse through
the interconnected semiconductor particles to the semiconductor particles-solution interface to oxidize Cl ions. The produced Cl and Cl2 radicals can participate in the degradation
of dye molecules adsorbed on the electrode surface or in the solution. At the same time, the electrons photogenerated in the
conduction band traverse through the interconnected semiconductor particles to the substrate, where they are withdrawn as
anodic photocurrents.
The mechanistic scheme leading to the degradation of Orange II
dye on WO3 film can be shown as follows:
(WO3 ) + h hvb + + ecb

k1

(2)

hvb + (holes in space charge layer) > hs + (trapped holes at the

WO3 film surface)

Figure 6: Dependence of the reciprocal initial photoelectrochemical degradation rate 1/r0 on the reciprocal initial concentration of Orange II dye 1/[Orange II], for a WO3 film electrode, under UV-Vis illumination (500 W), in 0.5 M NaCl supporting electrolyte, at E = 1.08 V vs. SCE.

hs + + OH ad OH ad + H+

k2

(3)

hs + + Cl ad Cl ad

k3

(4)

Cl ad + Cl ad Cl2 ad

k4

(5)

hs + + [Orange II] products

k5

(6)

OH ad + [Orange II] products

k6

(7)

Cl2 ad + [Orange II] products

k7

(8)

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Jin Luo et al./ J. New Mat. Electrochem. Systems 5, 315-321 (2002)

It can be assumed that k3 and k4 are higher than k2 because the

degradation rate of Orange II dye in the solution with Cl ions
is higher than in other media and also, the degradation rate is
higher at lower pH where the contribution of (3) is diminished.
The photoelectrochemical degradation of Orange II dye also occurs under illumination with visible light but the degradation
rates are lower than those under illumination with 500 W quartz
halogen lamp.
4.

CONCLUSION

Photoelectrochemical degradation of Orange II dye is faster and

more efficient than photocatalytic degradation. It is shown that
the photoelectrochemical degradation of Orange II dye is dominating over the electrochemical degradation path in the potential
range from E = 1.0 to E = 1.2 V. The mechanistic considerations lead to the conclusion that Orange II dye is mainly degraded through reactions with Cl and Cl2 radicals in NaCl
supporting electrolyte. The rate constant determined for photoelectrochemical degradation of Orange II dye on the WO3 film
electrodes is k = 2.9109 M cm2 s1 , at E = 1.08 V, in 0.5
M NaCl, under illumination of the UV-visible light.
5.

ACKNOWLEDGMENTS

This work was partially supported by the Petroleum Research

Fund of ACS, Grant No. 33190-B5.

[10] A. L. Linsebigler, G. Q. Lu, J. J. T. Yates, Chem. Rev., 95,

735 (1995).
[11] E. J. Weber, R. L. Adams, Environ. Sci. Technol., 29, 1163
(1995).
[12] K. Vinodgopal, P. V. Kamat, Chemtech, 26, 18 (1996).
[13] J. Bandara, C. Morrison, J. Kiwi, C. Pulgarin, P. Peringer,
J. Photochem. Photobiol. A-Chem., 99, 57 (1996).
[14] J. Fernandez, J. Bandara, A. Lopez, P. Buffat, J. Kiwi,
Langmuir, 15, 185 (1999).
[15] T. X. Wu, G. M. Liu, J. C. Zhao, H. Hidaka, N. Serpone,
J. Phys. Chem. B, 103, 4862 (1999).
[16] J. Fernandez, M. R. Dhananjeyan, J. Kiwi, Y. Senuma, J.
Hilborn, J. Phys. Chem. B, 104, 5298 (2000).
[17] V. Nadtochenko, J. Kiwi, J. Chem. Soc.-Faraday Trans.,
93, 2373 (1997).
[18] J. Fernandez, J. Bandara, A. Lopez, P. Albers, J. Kiwi,
Chem. Commun., 1493 (1998).
[19] J. Bandara, F. G. Herrera, J. T. Kiwi, C. O. Pulgarin, J.
Chem. Res.-S, 234 (1998).
[20] L. Lucarelli, V. Nadtochenko, J. Kiwi, Langmuir, 16, 1102
(2000).
[21] A. Lopez, J. Kiwi, Ind. Eng. Chem. Res., 40, 1852 (2001).

REFERENCES

[22] J. Bandara, J. Kiwi, New J. Chem., 23, 717 (1999).

[1] A. Mills, R. H. Davies, D. Worsley, Chem. Soc. Rev., 27

417 (1993).

[23] J. Bandara, J. A. Mielczarski, J. Kiwi, Langmuir, 15, 7680

(1999).

[2] S. Naskar, S.A. Pillay, M. Chanda, J. Photochem. Photobio. A: Chem., 113, 257 (1998).

[24] K. Vinodgopal, I. Bedja, S. Hotchandani, P. Kamat, Langmuir, 10, 1757 (1991).

[3] S. Lakshmi, R. Renganathan, S. Fujita, J. Photochem.

Photobio. A: Chem., 88, 163 (1995).

[25] K. Vinodgopal, P. Kamat, Environ. Sci. Technol., 29, 841

(1995).

[4] C. Nasr, K. Vinodgopal, L. Fisher, S. Hotchandani, A.K.

Chattopadhyay, P.V. Kamat, J. Phys. Chem., 100, 8436
(1996).

[26] F. Wu, N. S. Deng, H. L. Hua, Chemosphere, 41, 1233

(2000).

[5] K. Vinodgopal, D. E. Wynkoop, P.V. Kamat, Environ. Sci.

Technol., 30, 1660 (1996).
[6] M. Tomkiewicz, Catalysis Today, 58, 115 (2000).
[7] Z. Zhu, M. Lin, G. Dagan, and M. Tomkiewicz, J. Phys.
Chem., 99, 15950 (1995).
[8] B. Singhal, A. Porwal, A. Sharma, R. Ameta, S. C. Ameta,
J. Photochem. Photobio. A: Chem., 108, 85 (1997).
[9] N. Serpone, P. Maruthamuthu, P. Pichat, E. Pelizzetti,
H. Hidaka, J. Photochem. Photobio. A: Chem., 85, 247
(1995).

[27] M. R. Dhananjeyan, J. Kiwi, K. R. Thampi, Chem. Commun., 1443 (2000).

[28] M. R. Dhananjeyan, E. Fine, J. Kiwi, J. Photochem. Photobiol. A-Chem., 136, 125 (2000).
[29] J. Bandara, V. Nadtochenko, J. Kiwi, C. Pulgarin, Water
Sci. Technol., 35, 87 (1997).
[30] C. Bauer, P. Jacques, A. Kalt, Chem. Phys. Lett., 307, 397
(1999).
[31] J. Bandara, J. A. Mielczarski, J. Kiwi, Langmuir, 15, 7670
(1999).

Photoelectrochemical Degradation of Orange II Textile Dye. / J. New Mat. Electrochem. Systems 5, 315-321 (2002)

[32] J. Kiwi, A. Lopez, V. Nadtochenko, Environ. Sci. Technol.,

34, 2162 (2000).
[33] J. Luo, M. Hepel, Electrochim. Acta, 46, 2913 (2001).
[34] I. Shiyanovskaya, M. Hepel, J. Electrochem. Soc., 145,
3981 (1998).
[35] I. Shiyanovskaya, M. Hepel, J. Electrochem. Soc., 146,
243 (1999).
[36] I. Shiyanovskaya, M. Hepel, J. Electrochem. Soc., 145,
1023 (1998).
[37] I. Shiyanovskaya, M. Hepel, E. Tewksburry, J. New Mat.
Electrochem. Systems, 3, 241 (2000).
[38] J. Augustynski, C. Sartoretti, M. Ulmann, in Proc. Electrochem. Soc., Los Angeles, California, Vol. 96-1, p. 694
(1996).
[39] M. Hepel, J. Luo, Electrochim. Acta, 47, 729 (2001).
[40] C.S. Turchi and D.F. Ollis, J. Catal., 122, 178 (1990).

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