7174

Langmuir 2001, 17, 7174-7177

Influence of Carboxylic Acid on the

Photocatalytic Reduction of Cr(VI) Using
Commercial TiO2
G. Colon, M. C. Hidalgo, and J. A. Navo*
Instituto de Ciencia de Materiales de Sevilla, Centro Mixto
CSIC-Universidad de Sevilla, Avda. Americo Vespucio s/n,
41092 Sevilla, Spain
Received May 28, 2001. In Final Form: July 23, 2001

Introduction
Titania has universally been recognized as one of the
better photocatalysts in heterogeneous photocatalysis
applications as it combines two important complementary
features for a photocatalyst: good UV absorption efficiency
for the light harvesting process and good absorption
capacities, due particularly to the density of OH- groups
of amphoteric character. Many studies concern only the
catalytic activity of titanium oxide with single substrates.1
There are few papers concerning decontamination of
complex systems, which however are the actual situation
of the real environmental pollution.2,3Many waste streams
may contain mixtures of hazardous organic and inorganic
species. In fact, laboratory studies of these real mixtures
are a complex problem to resolve. H. Fu et al.4 reported
the simultaneous degradation of 4-chlorophenol and Cr(VI) in a synergic oxidation-reduction reaction. The
spontaneous reaction between these two toxic species
under environmental conditions is negligible. But Fu et
al. reported an important increase in the photocatalytic
degradation when the species are present at the same
time. From the point of view of the photocatalysis theory,
both oxidation and reduction reactions can take place
simultaneously by considering half redox semireactions
with the electron-hole pairs photogenerated, avoiding in
this way the possibility of recombination of these pairs
and therefore influenced synergically. Other interesting
examples were reported by S. Malato5 using a S2O82- agent,
and Y. B. Wang6 using periodate and persulfate as
sacrificial oxidants.
The interest in using carboxylic acids as complementary
reductants is that those compounds are considered as
common pollutants from industrial processes (metallurgy,
decontamination of nuclear plants and boilers, and textile
industries).7 In our previous study,8 although the increase
in the conversion rates for the simultaneous reactions
with respect to single ones was noteworthy, an important
deactivation process took place for commercial TiO2. Now,
we study the effect of different carboxylic acids in the
Cr(VI) photoreduction. We have also carried out the same
* Corresponding author. E-mail: navio@cica.es.
(1) Blake, D. Bibliography of work on the heterogeneous photocatalytic
removal of hazardous compounds from water and air: National
Renewable Energy Laboratory: Golden, CO, 1999.
(2) Fallmann, H.; Krutzler, T.; Bauer, R.; Malato, S.; Blanco, J. Catal.
Today 1999, 54, 309.
(3) Mansilla, H. D.; Yeber, M. C.; Freer, J.; Rodriguez, J.; Baeza, J.
Water Sci. Technol. 1997, 35, 273.
(4) Fu, H.; Lu, G.; Li, S. J. Photochem. Photobiol., A 1998, 114, 81.
(5) Malato, S.; Blanco, J.; Richter, C.; Braun, B.; Maldonado, M. I.
Appl. Catal., B 1998, 17, 347.
(6) Wang, Y. B.; Hong, C. S. Water Res. 1999, 33, 2031.
(7) Litter, M. I.; Navo, J. A. J. Photochem. Photobiol., A 1994, 84,
183.
(8) Colon, G.; Hidalgo, M. C.; Navo, J. A. J. Photochem. Photobiol.
2001, 138, 79.

Table 1. Surface and Structural Characterization of

Catalysts
catalyst

SBET
(m2/g)

St
(m2/g)

Vp
(cm3/g)

Dp
()

XA
(%)

Eg
(eV)

TiO2 Degussa
TiO2 Hombikat

51.0
289.0

47.0
282.0

0.15
0.34

315
35

80
100

3.5
3.5

experiences using N2 instead of O2 in order to state the

role of the gas used in the deactivation process observed
in the simultaneous reaction.
Experimental Section
Cr(VI) solution was prepared by using analytical grade K2Cr2O7 (Aldrich, 99%) at acid pH of about 1.5-2. H2SO4 was used
to set the correct pH value. Salicylic acid (Aldrich, 99+%) and
citric acid (Aldrich, 99+%) were prepared by dissolving the solids
in deionized water. Both solutions had a concentration of 4
10-4 M. For simultaneous degradation runs, a solution was
prepared by mixing the corresponding volume of each starting
solution of the single substrates. Therefore, the concentration of
the new solution was in this case 2 10-4 M in each pollutant.
The pH of the resulting solution was ca. 2. Degussa P25 and
Hombikat UV-100 (Sachtleben chemie) commercial titanium
dioxides were employed as received.
All catalytic runs were performed in a Pyrex immersion well
reactor. UV illumination of the reaction solutions was carried
out by using a medium pressure 400 W Hg lamp supplied by
Applied Photophysics. Oxygen and nitrogen flow was employed
in all cases to produce a homogeneous suspension of the catalyst
in the solution. Before each experiment, the catalysts (1 g/L)
were settled in suspension with the reagent mixture for 10 min.
The Cr(VI) concentrations were measured by means of UVvis spectroscopy, using the characteristic 290 nm band. About
2 mL of suspension was removed and filtered (Millipore Millex25
0.45 m membrane filter) previously to UV-vis spectral analysis.

Results and Discussions

Structure and Texture of Catalysts. Wide characterization of commercial TiO2 samples was reported in a
previous paper.8 Specific surface areas of as received
commercial titanium dioxide samples were determined
by means of the Brunauer-Emmett-Teller (BET) method.
In both cases, N2 isotherms could be assigned to type II
though a small hysteresis loop can be found. TiO2
Hombikat presents an intermediate shape between types
II and IV, with a hysteresis loop of namely type H4. From
pore distribution curves, a great difference in the pore
texture of both oxides can be seen. Table 1 summarizes
surface and structural characterization for both catalysts.
Worth noting is the significantly higher value of the surface
area for TiO2 Hombikat UV-100 compared to Degussa
P25. Pore volume is also greater than that observed for
Degussa P25, but the lower average pore diameter
indicates that Hombikat UV-100 particles are forming
small and compact aggregates, thus giving high surface
area. On the other hand, Degussa P25 can be thought to
form rougher particles with a porous surface, as was
observed by the scanning electron microscopy technique.8
The morphology of the Degussa sample is clearly different
from the Hombikat one.8 Thus, TiO2 Degussa presents a
wrinkled surface. On the other hand, Hombikat particles
are mainly spherical, formed by small subparticles highly
agglomerated. Therefore, the surface of these rounded
particles is full of small very pores producing the higher
specific surface area exhibited by Hombikat UV-100.
Regarding the structural feature, Degussa P25 shows
well-defined diffraction peaks corresponding to a phase

10.1021/la010778d CCC: $20.00 2001 American Chemical Society

Published on Web 10/04/2001

Notes

Langmuir, Vol. 17, No. 22, 2001 7175

Figure 1. Photocatalytic conversions for Cr(VI) photoreduction

using O2 flow for TiO2 Degussa P25 and TiO2 Hombikat UV100.
Table 2. Photon Efficiencies for Cr(VI) Photoreduction
in the Presence of Carboxylic Acid
photocatalyst
Degussa
Hombikat

atmosphere

single

salicylic acid

citric acid

O2
N2
O2
N2

8.5

32.5
20.6
40.4
23.3

34.7
37.4
31.9
43.1

10.6

mixture of anatase and rutile. However, TiO2 Hombikat

showed a rather amorphous diffraction pattern, with wider
peaks, indicating less crystallinity. In this case, the only
phase present is the anatase one. Anatase molar fractions
calculated from X-ray diffraction are summarized in Table
1.
From UV-vis diffuse reflectance spectroscopy, band gap
energies have been calculated (Table 1), being for both
photocatalysts close to 3.5 eV. Absorption is produced in
both cases at wavelengths lower than 400 nm.
Photocatalytic Properties. Figure 1 shows the photocatalytic conversion for Cr(VI) photoreduction using TiO2
Degussa and Hombikat under an oxygen flow. In both
cases, Cr(VI) photoreduction follows similar kinetic profiles. Both Degussa and Hombikat TiO2 arrive to almost
complete reduction, at the end of the experience. Photon
efficiencies calculated from these curves (Table 2) indicate
that the reaction proceeds similarly using TiO2 Degussa
and Hombikat catalysts, being slightly higher for Hombikat TiO2.
(a) Cr(VI) and Salicylic Acid Simultaneous Photodegradation. TiO2 Degussa P25 and Hombikat UV-100 were
tested for the simultaneous photodegradation of salicylic
acid and Cr(VI), in the presence of either oxygen or
nitrogen flow. After 10 min in which the photocatalyst
powders reach the equilibrium with the substrates to be
photodegraded, we have irradiated the suspension for 5
h. Figures 2 and 3 show the conversion value curves for
TiO2 Degussa P25 and Hombikat UV-100 tested for this
reaction in the presence of O2 and N2. In the presence of
oxygen flow (Figure 2), the photodegradation of Cr(VI)
and salicylic acid seems to proceed very rapidly. Photon
efficiencies for the simultaneous photodegradation present
very high values with respect to single reactions. However,
maximum conversion observed at the end of the experiment is not higher than 50% in the case of Degussa and
below 80% for Hombikat. Significant deactivation of the
photocatalyst is observed. In our previous paper,8 we have
tentatively explained this deactivation process by the

Figure 2. Photocatalytic conversions for Cr(VI) photoreduction

in the presence of salicylic acid and using O2 flow for (a) TiO2
Degussa P25 and (b) TiO2 Hombikat UV-100.

formation of certain Cr-complexes that would attach at

the surface of TiO2, blocking the photoprocesses. These
metal complexes would arise from the intermediate
photodegradation products of salicylic acid. In the case of
Hombikat, it was stated that different surface features
improve its photocatalytic properties giving up higher
conversion values. Photoreduction of Cr(VI) in the presence
of salicylic acid presents higher conversion rates than in
the single one. In the single photoreduction of Cr(VI),
dissolved oxygen competes very strongly with Cr(VI)
species for the photogenerated electrons, suggesting that
its presence is detrimental to the reduction of Cr(VI) to
Cr(III) as has been reported by other authors.9Thus, we
carried out the same photocatalytic experiences using a
pure nitrogen flow instead of oxygen (Figure 3). In this
case, conversion values are slightly higher than those
obtained in oxygen flow. Photon efficiencies calculated
from conversion curve slopes (Table 2) indicate however
that photoreactions carried out in the presence of pure O2
flow exhibit higher efficiencies, specially for the Hombikat
catalyst. Using nitrogen as the flowing gas, similar
efficiencies have been calculated for both catalysts,
indicating that catalyst feature is not a determinant factor
in this case. Therefore, the formation of the metal
complexes that deactivate the surface photocatalysts
should be aided by the presence of oxygen, the surface
and structural features of the photocatalyst being very
important in that case since the deactivation process could
take place. Thus, there is a double function of oxygen in
(9) Alam, M.; Montalvo, R. Metall. Mater. Trans. B 1998, 28.

7176

Langmuir, Vol. 17, No. 22, 2001

Notes

Figure 3. Photocatalytic conversions for Cr(VI) photoreduction

in the presence of salicylic acid and using N2 flow for (a) TiO2
Degussa P25 and (b) TiO2 Hombikat UV-100.

Figure 4. Photocatalytic conversions for Cr(VI) photoreduction

in the presence of citric acid and using N2 and O2 flow for (a)
TiO2 Degussa P25 and (b) TiO2 Hombikat UV-100.

the reaction: one positive, increasing the photon efficiencies, and one negative, leading to the formation of species
that would turn off the photoreaction.
(b) Cr(VI) and Citric Acid Simultaneous Photodegradation. Figure 4 shows the photocatalytic conversions for
TiO2 Degussa and Hombikat for the photodegradation of
Cr(VI) in the presence of citric acid. In both cases,
conversions for the photocatalytic reduction of Cr(VI)
arrive almost to the complete reduction to Cr(III). No
significant differences can be observed when the reaction
is carried out under N2, although in both cases conversion
values seem to be slightly higher. When these results are
compared with those reported in the above section, it is
clear that the nature of the carboxylic acid is rather
important in the reduction of Cr(VI). When the nonaromatic oligocarboxylic acid is used as the sacrificial agent,
TiO2 does not suffer any deactivation process, and
therefore surface characteristic is not the determinant
feature of the photocatalysts. Citric acid improves the
photon efficiency of Cr(VI) photoreduction, specially using
N2 as the flowing gas. However, results obtained for
Degussa are not so different for N2 and O2. The presence
of oxygen would be involved in this reaction, in the way
that it participates actively in the photodegradation,
competing directly with the Cr(VI) reduction. Only in the
case of the Hombikat photocatalyst is there a great
influence using nitrogen gas flow, the value being high
enough with respect to the value calculated from the
conversion curve in oxygen.
The mechanism of photodegradation of aromatics is
rather complex. There are many studies concerning the

mechanism followed by these organic compounds during

their photocatalytic oxidation.10,11 Aromatic compounds
trend to form quinone/hydroquinone and polyhydroxy
derivative (mainly dihydroxy) species at the first stages
of photodegradation, while the first step in the oxidation
of nonaromatic compounds is the formation of a double
bond by a dehydration process11 and successive cracking
of the molecule into a shorter one. Therefore, it would be
supposed that the formation of this derivative species from
the aromatic ring leads to the formation of metal complexes, probably at the surface, that deactivate the
catalyst. Photoreduction of Cr(VI) in the presence of citric
acid does not generate this kind of complexes, or at least
complexes created are not so harmful for photocatalyst
activity.
Structural and morphological comparison of two commercial TiO2 photocatalysts (Degussa P25 and Hombikat
UV-100) revealed that both oxides present different
crystalline structure as well as surface features. No
significant differences can be found in the light absorptive
properties.
The nature of the carboxylic acid used as the sacrificial
agent seems to have a very important role in the
photoreduction of Cr(VI). Oligocarboxylic acid with aromatic character seems to induce the deactivation of the
photocatalyst. Meanwhile, a nonaromatic carboxylic acid
such as citric acid leads to higher conversion rates without
(10) Pelizzetti, E.; Minero, C. Electrochim. Acta 1993, 38, 47.
(11) Herrmann, J. M.; Tahiri, H.; Guillard, C.; Pichat, P. Catal. Today
1999, 54, 131.

Notes

deactivation of the catalyst. The nature of the gas flow

applied to the photoreactor is also of great influence.
Nitrogen flow seems to avoid the formation of the species
that causes the deactivation observed for the Cr(VI)
photoreduction in the presence of salicylic acid. When citric
acid is present, nitrogen does not play the same role, and
in this case it does not affect so decisively the Cr(VI)
reduction, although photon efficiencies are still better,
specially for Hombikat UV-100. Further investigations

Langmuir, Vol. 17, No. 22, 2001 7177

are now in progress in order to elucidate more deeply

mechanistic information.

Acknowledgment. The authors thank NATO (Project

Ref. ENVIR.LG 971292) and FEDER Project 1FD97-0340
for supporting part of this work.
LA010778D