Solar Energy Materials & Solar Cells 76 (2003) 189199

Visible light-induced degradation of blue textile

azo dye on TiO2 =CdOZnO coupled
nanoporous lms
! a,
R. Sua! rez-Parraa,*, I. Herna! ndez-Pe! rezb, M.E. Rincon
a
!
S. Lopez-Ayala
, M.C. Rolda! n-Ahumadaa
! en Energ!a, Universidad Nacional Autonoma
!
Centro de Investigacion
de M!exico, Apartado Postal 34,
Temixco 62580, Morelos, Mexico
b
!
!
Universidad Autonoma
Metropolitana-A, Departimento de Ciencias Basicas,
Av. Sn. Pablo No. 180,
M!exico 02200, DF, Mexico

Received 28 January 2002; received in revised form 25 July 2002

Abstract
The photodegradation of a typical textile blue azo dye, followed by UVVIS spectra
analysis, has been carried out successfully under white light illumination on TiO2 =CdOZnO
nanoporous coupled thin lms. A relatively fast degradation occurs in dye solutions with
concentrations of 100 mg=l (pH 3), at temperatures of 851C; and with the aid of 400 mg=l
hydrogen peroxide. Photodegradation also occurs on nanoporous TiO2 lms but with
signicant lower efciency than on TiO2 =CdOZnO coupled nanoporous lms. Dye
photodegradation does not occur on TiO2 =CdO or TiO2 =ZnO nanoporous lms, suggesting
that both CdO and ZnO components are required on the sensitization of TiO2 nanoporous
lms. A combined effect of new sensitizing interband states (response to white illumination)
and/or rectication phenomena (improved charge separation) may be responsible of the higher
photocatalytic activity of the TiO2 =CdOZnO nanoporous lms. Similarly, the alternative
route for visible degradation, the photosensitized degradation mechanism, could also benet
from the coupled nanoporous lms due to a higher driving force for electron injection (dye
oxidation).
r 2002 Elsevier Science B.V. All rights reserved.
Keywords: Nanoporous lms; Semiconductor; Azo-dyes; Photodegradation; Wastewater; Photocatalysis

*Corresponding author.
E-mail address: rsp@cie.unam.mx (R. Su!arez-Parra).
0927-0248/03/$ - see front matter r 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 7 - 0 2 4 8 ( 0 2 ) 0 0 3 4 6 - X

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1. Introduction
Extensive studies to resolve the pollution of wastewater generated by the textile
industry have been done through chemical, biological and biochemical processes,
with different success and costs [1]. In some countries, the more stringent restrictions
on wastewater discharges have obligated the textile industry to reuse its treated water
and to develop substitutes for toxic chemicals [2]. The necessity of nding an
effective and economical process to clean wastewater from textile dyes has motivated
important research efforts on several aspects of the problem. The design and
development of new materials to support the emergent technologies is an important
aspect still to be addressed.
Recent works reported on the literature have focussed on the success of biological
processes in decolorizing azo dyes [3,4]. Regardless of their success, the biological
treatment has various disadvantages, among them the decolorizing reactions involve
aerobic and anaerobic processes which are necessary to deal with slow and costly
reactions (i.e., they usually take more than 24 h) and many reactants are required to
set up the catalytic conditions in the biological reactor.
Alternative processes to remove heavy metals and color from wastewater polluted
with azo dyes include chemical precipitation, adsorption on activated carbon,
membranes, catalytic oxidation, electrochemical processes, and oxidation treatments
with hydrogen peroxide, ozone or UV radiation. In particular, the use of
semiconductor oxides in photocatalytic processes has been successful in removing
different organic compounds from industrial wastewater [1,58]. In regard to the
photocatalytic destruction of azo dyes, the group of Kamat (see for example,
Ref. [9ae]) has reported promising results. Despite of this, the textile industry has
made limited use of photocatalytic processes. This industry has used photocatalysis
mainly as a nal polishing step or at low dye concentration, and only with few
semiconducting oxides candidates (silicon and iron oxides) [1,2].
The photocatalytic properties of polycrystalline TiO2 [5,1014], ZnO [15,16] and
CdO [16] are well known, particularly as emulsion powders. Furthermore, the
photocatalytic activity of their mixture/coupling has been explored in recent works
[9b, d] with the purpose of improving charge separation. The separation of
photogenerated carriers in coupled systems enhances the carriers lifetime and
consequently the amount of oxidizing and reducing species formed under
illumination. Regardless rectication phenomena (charge separation) is observed
and expected in multilayer congurations of appropriate semiconducting polycrystalline materials (relative band positioning is important), nanoporous lms are
not expected to behave as its polycrystalline counterparts. In nanoporous materials,
the large surface area of the lm and the nanometric size of the grains impose new
conditions on the semiconductor surface that are difcult to predict and must be
studied in detail.
In this work, we prepared nanoporous TiO2 =CdOZnO coupled lms to degrade
an azo dye from textile factories. We studied their photocatalytic properties and
compared them to the properties of more simple nanoporous lms like TiO2 ;
TiO2 =ZnO and TiO2 =CdO: Because we are interested in using visible light for the

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photodegradation process of residual azo dyes, the possibility of sensitization due to

interband states is also indirectly addressed.

2. Experimental details
2.1. Materials
Reactants titanium (IV) isopropoxide (97%) and acetic acid (99.99%) were
obtained from aldrich and 2-propanol, CdCl2 ; ZnCl2 ; H2 O2 were obtained from
Baker. The water used to prepare the solutions was puried in a Millipore (Milli-Q)
system.
2.2. Preparation of films
To prepare TiO2 nanoporous lms, a colloidal solution of TiO2 was prepared as
described by Kamats group [17]. Basically, it is a reaction of titanium isopropoxide
with acetic acid in isopropanol-aquous media to form the colloidal solution of TiO2 :
Afterwards, this solution was kept in an autoclave for 20 h at 2001C and 1520 atm:
An aliquot of 1/ml of the TiO2 colloidal solution was dropped on a 2 cm2 glass
substrate, and the solvent evaporated at 40501C: The TiO2 nanoporous lm acts as
a template for the subsequent growth of a ZnOCdO lm. This combined lm was
obtained by immersion in different saturated solutions containing Cd2 CdCl2 ;
Zn2 ZnCl2 ; and O2 H2 O2 at 30%) ions in a specic sequence: Zn2 /rinse/O2 /
rinse/Cd2 /rinse/ O2 /rinse. Immersion on saturated solutions lasted 5 min; while
rinsing with deionized water lasted 1 min: The cycle was repeated 5 times, after
which sintering of the lms is performed at 4501C in air for 2 h: For deposition of
pure CdO or ZnO, the number of cycles was maintained, but the sequence was
shortened by half (i.e., for CdO: Cd2 /rinse/O2 /rinse).
2.3. Photocatalytic reaction
The photocatalytic reaction took place in a 600 ml Pyrex ask, under acidic
conditions (pH 3; adjusted with diluted sulfuric acid (Baker, 99% solution)), and
with hydrogen peroxide as an oxidant aid (H2 O2 30%). The azo dye was obtained
from Novartis and used in relatively high concentrations (CAZO DYE 100 mg=l)
without further purication. The illumination was provided by a 50 W tungsten
halogen lamp (KOTAS), which was placed in the center of the ask and isolated
from the solution by a quartz tube. The white lamp output was B80 mW=cm2 at the
sample position and steadily increased the temperature in the reactor up to 851C:
Any water evaporated from the reactor was replaced with distilled water to keep the
initial volume at 500 ml: The TiO2 =CdOZnO nanoporous lms (two glass
substrates of 2 cm2 geometric area) were supported in a cylindrical acrylic basket
placed around the wall of the reactor to obtain a uniform radial radiation. A scheme
of the reactor used is given in Fig. 1.

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Fig. 1. Photocatalytic reactor used for photodegradation of textile azo dye.

The textile azo-dye identication was performed by Fourier transform infrared

spectroscopy (FTIR, BrukerEQUINOX 55), while its degradation was followed
by UVVIS spectroscopy (Shimadzu UV-3101PC) at 640 nm:

3. Results and discussion

The typical absorption band for the azo group in blue dyes is reported around
1433 cm1 ; while infrared absorption due to azoaryl compounds is expected around
1511 cm1 [9c]. These absorptions can be observed in the infrared spectrum of the
blue dye used in this work (Fig. 2), which is typical of the pollutants produced by the
textile industry. The photodegradation of this dye was followed by UVVIS
spectroscopy, using a calibration curve obtained at a frequency where LambertBeer
law shows good linearity for the concentration range of interest (25100 mg=l).
These results are shown in Fig. 3 at a wavelength of 640 nm; under the following
conditions: pH 3; CH2 O2 600 mg=l and T 251C: Hydrogen peroxide was used
for the photocatalytic process in combination with the semiconductor lms. The
optimum hydrogen peroxide concentration was xed after running the photodegradation reaction with different amounts of this oxidant.
The role of hydrogen peroxide in the photocatalysis of azo dyes by nanoporous
coupled lms is shown in Fig. 4. It can be seen that shorter degradation times are
required when increasing the hydrogen peroxide concentration from 200400 mg=l:
Larger amounts of hydrogen peroxide are detrimental to the photocatalytic process,
conrming what has been observed in other photocatalytic reactions carried out with
polycrystalline and nanoporous TiO2 lms [5]. The photocatalytic rate as a function
of hydrogen peroxide is shown as an inset in Fig. 4. The rate shown as the y-axis

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Fig. 2. Diffuse reectance FTIR spectrum of blue azo dye (lanasol blue).

Fig. 3. Absorption spectra of textile azo dye at various concentrations. The inset shows the calibration
curve obtained at 640 nm; under pH 3; CH2 O2 600 mg=l and T 251C:

represents the initial rate calculated by treating the photodegradation curve as two
linear regions, a fast decay (initial rate) followed by an asymptotic behavior. The
curve maximum is typical of a competitive process. It can be explained in terms of a
favorable role of hydrogen peroxide to continue the oxidation of the reaction
products and avoiding that they re-adsorb on the semiconductor surface, while at
higher concentration hydrogen peroxide can compete with the dye for adsorption

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Fig. 4. Textile azo-dye photodegradation on TiO2 =CdOZnO coupled nanoporous lms as a function of
H2 O2 concentration. The inset graphic shows the inuence of H2 O2 on the initial reaction rate.

sites. The optimal concentration of hydrogen peroxide under the present conditions
is around 400 mg=l:
In order to assess the photocatalytic performance of TiO2 =CdOZnO coupled
nanoporous lms, the photodegradation curve was compared with the one obtained
on TiO2 nanoporous lms (i.e., the template used for the growth of CdOZnO lms),
under optimum hydrogen peroxide concentrations. Fig. 5 shows the photodegradation curves of blue azo dye obtained with fresh and reused nanoporous lms: TiO2
(solid squares) vs. TiO2 =CdOZnO (open squares). For both fresh and reused lms,
the TiO2 =CdOZnO nanoporous lms show higher degradation rates than the TiO2
template. This difference, however, is magnied when the surface is fresh and tends
to be erased in reused lms indicating compositional and structural changes on the
active surface. The TiO2 =CdO and TiO2 =ZnO nanoporous lms did not show
photocatalytic activity under the white illumination conditions studied here,
suggesting that both CdO and ZnO components are required on the sensitization
of TiO2 nanoporous lms. Under the assumption that photon absorption takes place
mainly in the semiconductor lm, the superior photocatalytic activity of the
nanoporous coupled lms could be explained in terms of a combined effect of
rectication phenomena (improved charge separation) and response to white
illumination through the formation of new sensitizing interband states, perhaps
inclusion of Cd/Zn into ZnO/CdO, and/or new ternary compounds with lower band
gap. The lamp spectrum shown in Fig. 6 rules out band/band excitation from any of
the binary compounds, particularly in the form of nanoparticles, since their
polycrystalline counterparts report values of band gap superior to 3 eV (o400 nm).
The question of whether or not complete mineralization is obtained with
nanoporous coupled TiO2 =ZnOCdO lms requires rigorous analytical techniques.

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Fig. 5. Visible light-induced degradation of azo dye on fresh (1st) and reused (2nd) nanoporous lms:
TiO2 (solid squares), TiO2 =CdSZnS (open squares). Dye concentration and reactor conditions were the
same in all the curves shown: Cazo dye 100 mg=l; pH 3; CH2 O2 400 mg=l; and T 251C:

Fig. 6. Spectrum of the lamp used for photocatalytic degradation of azo dyes.

From the work reported on the literature on visible light-induced degradation of

textile azo dyes [9], the complete mineralization of these dyes is not achieved if only
the photosensitized degradation route is active. This route requires the excitation of
the dye by visible light, and enough driving force to inject electrons from the excited
state of the dye into the conduction band of the semiconductor particle. The driving
force is the energy difference between the oxidation potential of the excited dye and

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the conduction band of the semiconductor. Diffuse reectance FTIR experiments

performed by Kamats group [9c] have indicated that under the scheme of
photosensitized degradation the nal product for the degradation of naphthol blue
diazo dye is a quinone intermediate. Nevertheless, these authors expected complete
mineralization when using broad band illumination since the conventional
photocatalytic route (oxidation by hydroxyl radicals) can combine with photosensitized degradation. We must point out that the photosensitized degradation
mechanism requires the adsorption of the dye on the semiconductor lm and
consequently is very sensitive to the chemical composition of the surface. The lack of
photoactivity in TiO2 =CdO and TiO2 =ZnO nanoporous lms suggest either poor
dye adsorption or insufcient driving force for charge injection to occur. The
compositional changes in TiO2 =CdOZnO coupled nanoporous lms, discussed in
previous paragraphs from the point of view of inducing visible response in the
semiconductor lm (i.e., semiconductor with lower band gap or sensitizing interband
states), could also be thought as increasing the driving force required for the
photosensitized degradation. In other words, both mechanisms may be acting in
coupled nanoporous lms.
Fig. 7 shows the evolution of new features in the UVVIS spectrum of the azo dye
at different times of photodegradation. These results are sufcient to validate the
efciency of these semiconductor lms to remove color, even though the toxicity
issue remains questionable. Complete bleaching of the absorption band at 615 nm
takes place in 6 h; which is relatively fast when compared to the 42 h required on
TiO2 nanoparticles [9c] (complete bleaching was not pursue on the TiO2 templates
studied here). For the initial stages of degradation, the destruction of the
chromophore is accompanied by the formation of smaller fragments that absorb

Fig. 7. Absorption spectra recorded at different time intervals during the visible light degradation of azo
dyes. Degradation conditions were: Cazo dye 100 mg=l; pH 3; CH2 O2 400 mg=l; and T 851C:

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in the UV region, below 300 nm: After 2 h of visible photodegradation, the

absorption, in both visible and UV regions, decreases substantially indicating a more
complete degradation, but still some absorption is observed at 480 nm: The spectrum
after 4 h suggests the complete mineralization of the azo dye, particularly because at
the end of the reaction the initial pH 3 moves to 6. The build up of colorless
reaction products such as oxalate and/or formate has been reported for

Fig. 8. (a) Decay curves representing the azo-dye degradation under various conditions of temperature,
hydrogen peroxide and illumination. Symbol J used for the non-isothermal experiment due to build up
of heat during illumination and with hydrogen peroxide present since the start; symbol & used for the
isothermal run at 851C; where hydrogen peroxide was added after 4 h of illumination; symbol W
indicates non-illuminated isothermal run at 851C; with hydrogen peroxide since the start and illumination
turned on 4 h later. (b) Rate proles of the processes depicted in (a).

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photocatalytic, radiolytic and sonolytic degradation of textile dyes, where the

formation of such low molecular weight acids is consistent with the decrease in pH
[9e].
The decay on the absorption at 640 nm is shown in Fig. 8 as a function of
illumination and hydrogen peroxide. In all cases TiO2 =CdOZnO nanoporous lms
were in the reactor. The concentration of the textile azo dye was slightly different in
each experiment but this fact does not disturb the further behavior of the reaction.
The curve with circles represents a non-isothermal process with hydrogen peroxide
present at the beginning of the reaction. In this curve, the temperature increases from
251C up to 851C because of the build up of heat during illumination. The other
curves shown in Fig. 8 were taken under isothermal conditions, either by heating the
system up to 851C under ambient illumination, or by letting the illuminated system
to reach the steady-state value of 851C: The curve with squares corresponds to the
illuminated system without hydrogen peroxide. In absence of H2 O2 ; the curve shows
small degradation during a period of 4 h: That is not surprising under white light
illumination, and particularly when most of the oxidant radical production (OH*) is
trough water oxidation. The dramatic increase in photodegradation rate after
addition of hydrogen peroxide to the reactor is consistent with its role of minimizing
back reactions. Hydrogen peroxide avoids back reactions either by scavenging
electrons or by continuing the degradation of the products and avoiding its readsorption on the nanoporous lm. From the perspective of direct dye oxidation
(photosensitization pathway), hydrogen peroxide is required to scavenge photoinjected electrons, otherwise the recombination between injected electrons and the
cation radical of the dye results in regeneration of the pollutant. The other
isothermal degradation is described by the curve with up triangles. Here the reactor
contains hydrogen peroxide since the start and is kept under day dispersed
illumination at 851C: Once illuminated with visible light, the initial degradation rate
is substantially large. Fig. 8b shows the photodegradation rates obtained under the
conditions discussed above. Similar maximums are observed for the non-isothermal
run and the curve run isothermally at 851C but with hydrogen peroxide added later
on. On the contrary, the curve on steady-state conditions at 851C shows its initial
degradation rate substantially higher than the rest once it is illuminated. This
suggests that the role of temperature is minor when compared to the role of
hydrogen peroxide and illumination, which corroborates that semiconductormediated degradation is the dominant mechanism in the destruction of the dyes.

4. Conclusions
Visible light-induced degradation of blue azo dyes has been carried out on
TiO2 =CdOZnO nanoporous coupled lms. UV and VIS spectrophotometric
analysis and the pH of the nal solution (pH changes from 3 to 6) support the
idea of complete mineralization of textile azo dyes in the proposed conditions. The
inferior photocatalytic activity of nanoporous TiO2 under white light illumination,
and its absence on TiO2 =CdO and TiO2 =ZnO nanoporous lms, indicates that both

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CdO and ZnO components are required for an optimum performance. Further
studies have to be done on wastewaters from textile factories to demonstrate the
feasibility of the material proposed here.

Acknowledgements
The authors thank to J.I. Herna! ndez and S. Ort!z-Jua! rez for technical assistance
in this work. The nancial support of DGAPA-UNAM (Projects IN110598 and
IN109200) and FIES-IMP (Project 98-47-III) are gratefully acknowledged.

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