Applied Catalysis B: Environmental 22 (1999) 83–90

Electrochemically assisted photocatalytic degradation of reactive dyes

Ronaldo Pelegrini a,∗ , Patricio Peralta-Zamora b , Adalgisa R. de Andrade c , Juan Reyes a ,
Nelson Durán a
a Universidade Estadual de Campinas, Instituto de Quı́mica, C.P. 6154, CEP: 13083-970, Campinas-SP, Brazil
b Universidade Federal do Paraná, Departamento de Quı́mica, Curitiba-PR, Brazil
c Departamento de Quı́mica da FFCLRP-USP, Riberão Preto-SP, Brazil

Received 3 June 1998; received in revised form 17 March 1999; accepted 18 March 1999

Abstract
The aim of this study was to investigate the efficiency of the electrochemically assisted photocatalytic process in the
degradation of C. I. Reactive Blue 19 on a Ti/Ru0,3 Ti0,7 O2 electrode. By using the quartz device and the Ti-supported
noble metal oxide coating, decolorizations ratios higher than 95% and TOC reduction of about 52% were observed during
a period of 120 min. Comparing this value with the sum of the decolorization ratios obtained by a single application of
electrochemical and photochemical procedures, it is possible to observe a significant synergic effect between both processes.
The electrochemical process was conduced at 28◦ C (refrigeration with air) and pH of 11.0, and with a constant potential
of 1.8 V versus Ag/AgCl. With these conditions, the mean current was 23 mA. The voltammetric results also confirm the
synergic effect of the simultaneous process. ©1999 Elsevier Science B.V. All rights reserved.
Keywords: Advanced oxidation technologies; Textile industry wastewater; Electrochemical oxidation; Photocatalysis; Mixed Ti–Ru oxides

1. Introduction action with the fiber and reduces energy consumption

The textile activities have a high potential envi-
ronmental impact, principally due to the release of
large volumes of wastewaters that contain high organic
charge and strong coloration [1]. Many dyes used in
textile processes show toxicity to the aquatic biota (or
can be biologically transformed to toxic species) and
could cause interference in natural photosynthetic pro-
cesses.
Reactive dyes are extensively used in the textile in-
dustry, fundamentally due to the capacity of their reac-
tive groups to bind on textile fibers by covalent bonds
formation [2]. This characteristic facilitates the inter-
∗ Corresponding author.
[3]. Reactive dyes represent an important fraction of
the commercialized synthetic pigments used (approx-
imately 12% of the worldwide production [4].
The major environmental problem associated with
the use of the reactive dyes is their loss in the dye-
ing process. Frequently, the fixation efficiency range
between 60% and 90% [3]; consequently, substantial
amounts of unfixed dyes are released in the waste-
water. In the particular case of the Reactive Blue 19,
the relatively low fixation efficiency (75–80%) is due
to the competition between the formation of the re-
active form (vinyl sulfone) and the hydrolysis reac-
tions (see Fig. 1). The latter reaction leads to the
formation of 2-hidroxyethylsulfone does not fix on the
fiber [2].

0926-3373/99/$ – see front matter ©1999 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 6 - 3 3 7 3 ( 9 9 ) 0 0 0 3 7 - 5
84 R. Pelegrini et al. / Applied Catalysis B: Environmental 22 (1999) 83–90
Fig. 1. Competition between formation of reactive and hydrolyzed forms of Reactive Blue 19 [2].
Unfortunately, the traditional processes used to treat
wastewater from textile industry do not remove these
compounds efficiently. Therefore, about 20% of the
unfixed dye are discharged into the environment [2].
The efficiency of heterogeneous photocatalytic pro-
cesses for degradation of many persistent chemicals
has been extensively documented, specially with the
use of titanium dioxide [5,6]. Recently, several pa-
pers on photochemical degradation of isolated dyes
have been published [7,8]. Similarly, electrochemical
oxidation of wastewater has been proposed for sev-
eral residue treatments [9], mainly due to its effective-
ness and operational facility [10]. The electrochemical
process has showed high efficiency for color removal
and for degradation of recalcitrant pollutants such as
cyanide, EDTA and aniline [10]. An interesting review
about electrochemistry and the environment was re-
cently published [11]. Unfortunately, the poor current
efficiency of the materials actually available in large
scale make this process not economically viable for
application in industrial plants.
In the seventies, Fujishima and coworkers proposed
the use of a single-crystal rutile-TiO2 photoanode for
photoelectrolytic decomposition of water [12]. Many
other procedures for photoelectrochemical oxidation
of organic pollutants have been reported [13–15].
In this work, an electrochemically assisted photo-
catalytic degradation of C.I. Reactive Blue 19 on a
dimensional stable anode (DSA® ), Ti/Ru0,3 Ti0,7 O2
electrode is reported. The use of a Ti-supported noble
metal oxide coating shows the following advances.
1. When the electrochemical (Ru) and the photo-
chemical (Ti) catalysts are immobilized on the
electrode, a large improvement was observed
compared with the use of heterogeneous cata-
lyst, (e.g., TiO2 suspension on photo cleavage of
water) since the catalyst separation step can be
eliminated [16].
2. Low cost of the electrodes.
3. Ti/Ru0,3 Ti0,7 O2 is commercially available.
It is also important to emphasize that the application
of an external anodic bias to drive the photogenerated
 R. Pelegrini et al. / Applied Catalysis B: Environmental 22 (1999) 83–90
electrons can considerably improve the efficiency of
the oxidation process [13,15]. The photoassisted elec-
trochemical degradation of several chemical species
has been demonstrated before [17–19], but as far as
we know the use of DSA® anodes is unexplored al-
ternative.
2. Experimental
2.1. Chemicals
Titanium plates were purchased from Ti-Brasil
Titânio Ltda. (Brazil). The anthraquinone dye C.I.
Reactive Blue-19 was purchased from a textile mill lo-
cated in Americana (São Paulo, Brazil). Dye solutions
were prepared with distilled water in concentrations
of 30 mg l−1 and pH 11.
Ruthenium and titanium chlorides (Aldrich) were
used without any further purification.
The precursor solution was composed of TiCl4
0.2 mol l−1 and RuCl3 ·2H2 O 0.2 mo l−1 (70 : 30, v/v)
dissolved in HCl 1 : 1 (v/v).
2.2. Electrodes
The working electrode of nominal composition
Ti/Ru0.3 Ti0.7 O2 was prepared by thermal decompo-
sition of the respective precursor solution at 450◦ C.
The coating was produced by thermal decompo-
sition of 70 mol% TiCl4 (Vetron) and 30 mol %
RuCl3 ·nH2 O dissolved in HCl aqueous solution (1 : 1,
v/v). This solution was brushed over a fresh Ti Plate
(20 mm × 25 mm × 0.85 mm) prepared by the usual
methods (sand blasting, degreasing, etching and rins-
ing, see for example [20,21]. After solvent evapora-
tion, the layer was fired for 5 min under 5 dm−3 m−1
O2 stream in a preheated furnace at 450◦ C. This
brush/fire procedure was repeated until the oxide load-
ing reached a nominal thickness of 2 mm, which cor-
responds to 1.01 mg cm−2 of the oxide mixture. The
electrode was finally fired for 1 h at 450◦ C. For elec-
trolysis, two Ti grids of 15 mm × 25 mm × 1.0 mm lo-
cated at both sides of the anode, was used as cathodes.
2.3. Instrumental
Electrochemical measurements were carried out in
a E.G. & G PAR model 273-A potentiostat with a stan-
dard three-compartment cell consisting of a Pt wire
85
gauze counter electrode and a Ag/AgCl electrode as
reference. The electrochemical behavior of the elec-
trode surface was investigated by cyclic voltamme-
try (CV), at 20 mV s−1 , between 0.2 and 1.0 V versus
Ag/AgCl, using a 1.0 mol dm−3 HClO4 solution.
The electrochemically assisted photochemical treat-
ments were carried out in a quartz (or Pyrex glass)
reactor, equipped with two 250 W medium-pressure
mercury lamps (Philips) located a distance of 6.0 cm
from the reactor quartz wall. The process was con-
duced at 28◦ C (refrigeration with air) and the poten-
tial was kept constant at 1.8 V versus Ag/AgCl. Under
these conditions, the mean current was 23 mA.
The electrochemical characterization of the dye
solution was carried out in a photochemical reactor
equipped with the working electrode (Ti/Ru0.3 Ti0.7 O2
– anode), a titanium grid (cathode) and an Ag/AgCl
reference electrode. The measurements were per-
formed at room temperature (water refrigeration) and
continuous magnetic stirring. A mercury lamp was
introduced in the dye solution and in the proximity of
the electrodes by using a quartz tube.
2.4. Analytical control
The efficiency of the process was evaluated by mon-
itoring the dye decolorization at the maximum ab-
sorption wavelength of 590 nm with a Hitachi U-2000
spectrophotometer and the total organic carbon reduc-
tion was measured with a TOC-5000 Shimadzu Total
Organic Analyzer.
Chromatographic determinations were performed
with a Shimadzu LC-10AD chromatograph (column:
ODS Hypersil (4 mm × 100 cm); detector: UV–Vis
(λ: 254 nm)). The mobile phase was composed of
5.0 × 10−4 mol l−1 H2 SO4 and acetonitrile (80 : 20
v/v).
Scanning electron micrographies were obtained on
a JEOL JSM-P15 reflection electronic microscope.
3. Results and discussion
3.1. Micrographic characterization
Fig. 2 shows the micrography obtained for the
modified electrodes. The pattern observed is the well-
known cracked-mud structure [22]. By monitoring
the concentration of atomic ruthenium and titanium
86 R. Pelegrini et al. / Applied Catalysis B: Environmental 22 (1999) 83–90

since the first step of the oxygen evolution in basic

medium is the hydroxyl ions discharge (Eq. (1)).
MOx + OH− → MOx (• OH) + e− (1)
where M: Ruthenium oxide active site.

Fig. 2. SEM images of a Ti/Ru0.3 Ti0.7 O2 as-prepared. Magnifica-

tion (× 1000).

by X-ray photoelectron spectroscopy (XPS), in four

random regions, a mean electrode composition of
30% (for Ru) and 70% (for Ti) was observed. This
electrode coating forms upon annealing in oxygen
atmosphere a solid solution of a thermodynamically
stable rutile structure.

3.2. Electrochemical characterization of the modified

electrode

The electrochemical behavior of the Ti/Ru0,3 Ti0,7 O2

electrode was characterized in a test electrolyte so-
lution (1.0 mol l−1 HClO4 ) to check the coating
conditions. The cyclic voltammogram obtained are
similar to the one reported by Galizzioli et al. [23],
e.g., the charge is distributed over a wide range of
electrode potential with two pair of bands located at
0.3–0.4 V and 0.9 V versus Ag/AgCl corresponding,
respectively, to Ru(III)/Ru(IV) and Ru(IV)/Ru(VI)
solid-state redox transitions.
In Fig. 3(A), shows the cyclic voltammogram ob-
tained for an unbuffered pH 11 solution of the dye
(30 mg l−1 ). Comparing this CV with a blank solu-
tion a perfect overlap is obtained however, no peak
related to the dye oxidation was observed. Compared
with the test solution, at pH 11 and low supporting
electrolyte the electrode surface charge is much lower
and any band related to solid-state redox transition is
observed in the double layer region (0.2–0.6 V versus
Ag/AgCl).
As reported before, in basic medium, the OER is Fig. 3. Current-potential behavior of the TiO2 modified electrode.
displaced to less positive potentials [24]. The electro- Effect of the modification with ruthenium (A), the time of use (B)
chemical process is favored in the alkaline medium and the UV irradiation application (C).
 R. Pelegrini et al. / Applied Catalysis B: Environmental 22 (1999) 83–90
Since a perfect overlap was observed in the pres-
ence and in the absence of the dye and taking in ac-
count the chemical analysis reported below we might
conclude that current increase observed at potentials
higher than 700 mV versus Ag/AgCl, in Fig. 3(A) is
due the oxygen evolution reaction (OER) plus dye ox-
idation (it = iO2 + idye ).
As expected, no electrochemical response was ob-
served for the metalic titanium electrode (Fig. 3(A)),
since the insulating TiO2 is formed on the Ti-surface
[25].
The high electrocatalytic activity of RuO2 [10] cou-
pled with the oxygen evolution reaction can be very
favorable for the photochemical degradation process.
As showed in Fig. 3(B) at elevated life time (50 h),
under accelerated corrosion conditions (Eap = 1.8 V
versus Ag/AgCl), the electrode charge is decreased.
Two hypotheses can be formulate to explain this elec-
trode deactivation: (i) formation, in basic solution and
1.8 V, soluble RuO4 [26] which may lead to a rich
insulatingTiO2 -coating, (ii) coating deactivation by a
organic film formed at the electrode surface. This film
would be a consequence of partial oxidation of the
dye.
In the voltammograms showed in Fig. 3(C) it is pos-
sible to observe that in the presence of UV-light, the
oxygen evolution reaction is displaced toward less pos-
itive potential and the current is also increased. That
is, for generation of a current of about 5 mA the non-
irradiated system needs a potential of about 1000 mV,
while in the irradiated one the required potential is near
of 700 mV therefore, there is a gain of 300 mV. This
is clear evidence of a synergetic effect between photo-
chemical and electrochemical process. The superox-
ides (O2 •− ) formed during the photochemical process
can produce additional amounts of hydroxyl radicals,
through the following sequence [27]. The photochem-
ical process can enhance the yields of radical interme-
diates formed during electrochemical O2 production.
The photochemical process is showed below:
O2 + e− → O2 •−
O2 + H+ → HO2 •
HO2 • + HO2 • → H2 O2 + O2
H2 O2 + e− → OH∗ + OH−
87
3.3. Decolorization study
From the results showed in Fig. 4, it is possible to
make the following observations: When the dye was
submitted to a single irradiation process a constant de-
colorizations ratios of about 3% was obtained in the
Pyrex reactor (Fig. 4(B)) for the whole period inves-
tigated (120 min). When the quartz device was used
(Fig. 4(A)) the degradation rate at 60 min increases to
15%. Since quartz reactor allows higher energy pho-
tons (UV) to impinge upon the solution we might con-
clude that short-wavelength ultraviolet light is respon-
sible for the photochemical degradation.
When the single electrochemical process (any light
source) was applied with an Eap = 1.8 V, a continuous
decay of the decolorization rate was observed with
a decolorization ratio of about 34% after a period
of 60 min. The following electrochemical mechanism
was proposed in the literature for organic degradation
[28]:
MOx + OH− → MOx (OH• ) + e− (2)
MOx (• OH) + D → xCO2 + xe− + zH+ (3)
MOx (• OH) + D → 1/2O2 + e− + MOx (4)
where D: dye.
As stated by Comninellis and De Battisti [28] the
high active OH• radicals adsorbed at ruthenium ox-
ide surface is formed is very reactive towards organic
degradation.
By using the quartz device plus applying the elec-
trochemically assisted photochemical process during
60 min, decolorizations ratios higher than 95% were
observed. By comparing this value with the sum of
the decolorization ratios obtained by a single applica-
tion of electrochemical (34%) and photochemical pro-
cedures (15%), it is possible to observe a significant
synergic effect on the electrochemically assisted pho-
tocatalytic process. This synergism can be explained
in term of: (1) in the presence of high energy pho-
tons (UV-light) the external bias can contribute to the
diminution of the electron – hole par recombination
process. (2) The UV-photons reaches the electrode sur-
face during electrochemical steps and can form ex-
cited radicals MOx (• OH)∗ which can enhance the dye
degradation.
88 R. Pelegrini et al. / Applied Catalysis B: Environmental 22 (1999) 83–90

Fig. 4. Color evolution by irradiation, electrochemical and electrochemically assisted photochemical processes. 30 ppm aqueous dye solution;
pH: 11.0; fresh electrode. (A): Utilization of a quartz device. (B): Utilization of a Pyrex device. (C): Net dye decolorization.

3.4. Degradation study promote a reliable chemical modification of the dye.

The dye sample, which corresponds to a technical
grade product, present an initial composition charac-
terized by six chromatographic peaks which probably
correspond to the hydrolyzed forms of the original
compound. In general, by monitoring the dye degra-
dation by liquid chromatography (results not shown) it
was observed that all the single processes investigated
Nevertheless, a significant degradation process was
observed only for the electrochemically assisted pho-
tochemical process after a reaction time of 120 min.
A similar conclusion can be reached by considering
the reduction of total organic carbon content (Table 1).
The isolate irradiation and electrochemical processes
permit TOC reduction of about 10% after a time of
120 min, while the combined process leads to a TOC
 R. Pelegrini et al. / Applied Catalysis B: Environmental 22 (1999) 83–90
Table 1
Reduction of the total organic carbon contenta
Process TOC reduction (%)
UV irradiation (Pyrex reactor) 2.5
UV irradiation (quartz reactor) 7.2
Electrolysis 9.6
UV irradiation (quartz) with eletrodes 10.0
Photoassisted electrolysis (Pyrex) 26.0
Photoassisted electrolysis (quartz) 52.0
a Dye concentration: 30 mg l−1 , treatment time: 120 min.
reduction of approximately 50% for an identical time.
Again, the efficiency of the combined process was
markedly reduced when the Pyrex device was used.
4. Final remarks
The results obtained in this exploratory study indi-
cate that the efficiency of the photochemical procedure
can be significantly improved by applying a simulta-
neous electrochemical process. The utilization of this
combined process permit almost total decolorization
of the C.I. Reactive Blue 19 and mineralization of
about 50% for a reaction time of 120 min. In view of
these results, the use of a Ti/Ru0,3 Ti0,7 O2 in an elec-
trochemically assisted photochemical process appears
to be a promising alternative for treatment of wastes
with high content of recalcitrant reactive dyes.
Acknowledgements
Support from CNPq is acknowledged.
References
[1] K.T. Fletcher, Design, the environment and textiles:
Developing strategies for environmental impact reduction, J.
Text. Inst. 89 (1998) 72–80.
[2] J. Weber, V.C. Stickney, Hydrolysis kinetics of Reactive Blue
19-vinyl sulfone, Water Res. 27 (1993) 63–67.
[3] R. Camp, P.E. Sturrock, The identification of the derivatives
of C.I. Reactive Blue 19 in textile wastewater, Water Res. 24
(1990) 1275–1278.
[4] K.W. Scharmm, M. Hirsch, R. Twelve, O. Hutzinger, A new
method for extraction of C.I. Reactive red 4 and its derivatives
from water, Water Res. 23 (1988) 1043–1045.
[5] M.R. Hoffmann, S.T. Martin, W. Choi, D.W. Bahnemann,
Environmental Applications of Semiconductor Photocatalysis,
Chem. Rev. 95 (1995) 69–96.
89
[6] A.L. Linsebigler, L. Guangquan, J.T. Yates Jr., Photocatalysis
on TiO2 surfaces: principles, mechanisms and selected results,
Chem. Rev. 95 (1995) 735–758.
[7] K. Vinodgopal, P.V. Kamat, Photochemistry of textile azo
dyes. Spectral characterization of excited state, reduced and
oxidized forms of acid orange 7, J. Photochem. Photobiol.
A. Chem. 83 (1994) 141–146.
[8] K. Vinodgopal, D.E. Wynkoop, P.V. Kamat, Environmental
photochemistry on semiconductor surfaces: photosensitized
degradation of a textile azo dye, acid orange 7, on TiO2
particles using visible light, Environ. Sci. Technol. 30 (1996)
1660–1666.
[9] F. De Angelis, C.R. Corso, E.D. Bidoia, P.B. Moraes,
R. Domingos, R.C. Rocha-Filho, Eletrólise de resı́duos
poluidores I. Efluente de uma indústria liofilizadora, Quı́mica
Nova 21 (1998) 20–24.
[10] C. Chiang, J.E. Chang, T.C. When, Indirect oxidation effect
in electrochemical oxidation treatment of landfill leqchate,
Water Res. 29 (1995) 671–678.
[11] K. Rajeshwar, J.G. Ibanez, G.M. Swain, Electrochemistry and
the environment, J. Appl. Electrochem. 24 (1994) 1077–1091.
[12] M. Wahl, A. Carroy, B. Jermann, M. Dolata, P.
Kedzierzawski, C. Chatelain, A. Monnier, J. Augustynski,
Photoelectrochemical studies pertaining to the activity of
TiO2 towards photodegradation of organic compounds, J.
Electroanal. Chem. 396 (1995) 41–51.
[13] H. Hidaka, H. Nagaoka, K. Nohara, T. Shimura, S.
Horikoshi, J. Zhao, N. Serpone, A mechanistic study of the
photoelectrochemical oxidation of organic compounds on a
TiO2 /TCO particulate film electrode assembly, J. Photochem.
Photobiol. A: Chem. 98 (1996) 73–78.
[14] J.M. Kesselman, N.S. Lewis, M.R. Hoffmann,
Photoelectrochemical degradation of 4 chlorophenol at TiO2
electrodes: comparison between sorption and photoreactivity,
Environ. Sci. Technol. 31 (1997) 2298–2302.
[15] K. Vinodgopal, S. Hotchandani, P.V. Kamat, Electro-
chemically assisted photocatalysis. TiO2 particulate film
electrodes for photocatalytic degradation of 4-chlorophenol,
J. Phys. Chem. 97 (1993) 9040–9044.
[16] P. Peralta-Zamora, E. Esposito, J. Reyes, N. Durán,
Remediação de efluentes derivados da indústria de papel e
celulose. Tratamento biológico e fotocatalı́tico, Quı́mica Nova
20 (1997) 186–190.
[17] K. Vinodgopal, P.V. Kamat, Enhanced rates of photocatalytic
degradation of an Azo Dye using SnO2 /TiO2 coupled
semiconductor thin films, Environ. Sci. Technol. 29 (1995)
841–845.
[18] K. Vinodgopal, P.V. Kamat, Combine electrochemistry with
photocatalysis, Chemtech April 26(4) (1996) 18–22.
[19] K. Vinodgopal, I. Bedja, P.V. Kamat, Nanostructured
semiconductor films for photocatalysis. Photoelectrochemical
behavior of SnO2 /TiO2 composite systems, and its role in
photocatalytic degradation of a textile azo dye, Chem. Mater.
8 (1996) 2180–2187.
[20] J.F.C. Boodts, S. Trasatti, Effect of composition on the
electrocatalytic activity of the ternary oxide, J. Electrochem.
Soc. 137 (1990) 3784–3789.
90 R. Pelegrini et al. / Applied Catalysis B: Environmental 22 (1999) 83–90
[21] G. Lodi, E. Sivieri, A. De Battisti, S. Trasatti, Ruthenium
dioxide-based film electrodes. III. Effect of chemical
composition and surface morphology on oxygen evolution on
acid solutions, J. Appl. Electrochem. 8 (1978) 135–143.
[22] K. Kameyama, K. Kaukada, K. Yahikozawa, Y. Takassu,
The application of scanning auger microscopy to the surface
characterization of RuO2 –TiO2 coated titanium electrodes, J.
Electrochem. Soc. 140 (1993) 966–969.
[23] D. Galizzioli, F. Tantardini, S. Trasatti, Ruthenium dioxide: a
new material I. Behavior in acid solution of inert electrolytes,
J. Appl. Electrochem. 4 (1974) 57–67.
[24] L.D. Burke, J.F. Healy, The importance of the reative surface
groups with regard to electrocatalytic behaviour of oxide
anodes, J. Electroanal. Chem. 124 (1981) 327–332.
[25] S. Trasatti (Ed.), Electrodes of Conductive Metallic Oxides,
Part a, Elsevier, Amsterdam, 1980.
[26] R. Kötz, S. Stucki, D.S. Cherson, D.M. Kolb, In-situ
identification of RuO4 as the corrosion product during oxygen
evolution on Ruthenium in acid media, J. Electroanal. Chem.
172 (1984) 211–219.
[27] R.L. Ziolli, W.F. Jardim, Mecanismo de Fotodegradação de
Compostos Orgânicos Catalisada por TiO2 , Quı́mica Nova
21(3) (1998) 319–325.
[28] C. Comninellis, A. De Battisti, Electrocatalysis in anodic
oxidatives of organic with simultaneous oxygen evolution, J.
Chim. Phys. Phys.-Chim. Biol. 93 (1996) 673–679.