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Heterogeneous photocatalysis of Cr(VI) in the presence of citric

acid over TiO2 particles: Relevance of Cr(V)citrate complexes
Jorge M. Meichtry a, Marta Brusa b, Gilles Mailhot c, Mara A. Grela b, Marta I. Litter a,d,*
a

Unidad de Actividad Qumica, Centro Atomico Constituyentes, Comision Nacional de Energa Atomica,
Av. Gral. Paz 1499, 1650 San Martn, Prov. de Buenos Aires, Argentina
b
Departamento de Qumica, Universidad Nacional de Mar del Plata, Funes 3350, B7602AYL Mar del Plata, Argentina
c
Laboratoire de Photochemie Moleculaire et Macromoleculaire, UMR 6505 CNRS, Universite Blaise Pascal, 63177 AUBIERE Cedex, France
d
Escuela de Posgrado, Universidad de Gral. San Martn, Peatonal Belgrano 3563, 18 piso, 1650 San Martn, Prov. de Buenos Aires, Argentina
Received 30 May 2006; received in revised form 14 August 2006; accepted 1 September 2006

Abstract
TiO2-photocatalytic reduction experiments of Cr(VI) (0.8 mM) under near UV (366 nm) irradiation in the presence of citric acid (0
[citric
acid] (mM)
40) were performed at pH 2 under air bubbling. Addition of citric acid facilitates Cr(VI) reduction, hindering the electron-shuttle
mechanism taking place in pure water. TOC monotonously decreases until all Cr(VI) was reduced. The maximum rate of Cr(VI) reduction was
attained for an initial citric acid/Cr(VI) molar ratio, R, equal to 1.25, a further increment in R being detrimental; however, Cr(VI) decay in the
presence of citric acid was always faster than in its absence. Cr(VI) reduction takes place through Cr(V) species, readily complexed by citrate and
detected by EPR spectroscopy. Quantitative EPR determinations indicate that an important fraction (nearly 15%) of the reduced Cr(VI) is
transformed to Cr(V)Cit, which also undergoes a photocatalytic transformation. The detrimental effect taking place at high conversions for
R > 1.25 can be ascribed to secondary steps, i.e., the competition between Cr(VI) and Cr(V) complexes for conduction band electrons or to the
competition of Cr(V)Cit and Cit for holes.
# 2006 Elsevier B.V. All rights reserved.
Keywords: Heterogeneous photocatalysis; TiO2; Cr(VI); Cr(V); Citric acid

1. Introduction
Industrial processes such as leather tanning, paint making
and others make chromium(VI) to be present as a frequent
pollutant in wastewaters [1,2]. Due to its acute toxicity and high
mobility in water, Cr(VI) is in the list of priority pollutants of
many countries in the world [35]. Its treatment is performed
generally by transforming Cr(VI) to the less noxious Cr(III),
which is considered non-toxic and an essential trace metal in
human nutrition. Furthermore, Cr(III) can be precipitated and
removed as a solid waste. Among various reductive methods,
photocatalysis with TiO2 or similar photoactive materials has
been the object of various studies in recent times [1 and
* Corresponding author at: Unidad de Actividad Qumica, Centro Atomico
Constituyentes, Comision Nacional de Energa Atomica, Av. Gral. Paz 1499,
1650 San Martn, Prov. de Buenos Aires, Argentina. Tel.: +54 11 6772 7016;
fax: +54 11 6772 7886.
E-mail address: litter@cnea.gov.ar (M.I. Litter).

references therein, 610]. Many industrial and natural waters

contain also organic compounds such as oligocarboxylic acids,
and it has been largely demonstrated that the addition of organic
donors able to act as hole scavengers or to chelate to the TiO2
surface accelerates Cr(VI) reduction in photocatalytic systems,
the synergy being dependent on the nature of the reducing agent
[1123].
In previous works [2,24] we experimentally demonstrated
for the first time the formation of Cr(V) complexes in the
heterogeneous photocatalytic reduction of chromium(VI) over
TiO2 in the presence of oxalic acid and of EDTA. It was
proposed that successive one-electron steps passing through
reduced chromium species compose the general pathway for
Cr(VI) photocatalytic reduction. Moreover, ligands able to
form complexes with Cr(III) and Cr(V), an already proved
intermediate in the reduction of Cr(VI) in many processes, play
an especial role in the process.
On the other hand, Cr(V) chemistry has recently received a
lot of attention since their complexes with biomolecules are

0926-3373/$ see front matter # 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcatb.2006.09.002

Please cite this article as: Jorge M. Meichtry et al., Heterogeneous photocatalysis of Cr(VI) in the presence of citric acid over TiO2 particles:
Relevance of Cr(V)citrate complexes, Applied Catalysis B: Environmental (2006), doi:10.1016/j.apcatb.2006.09.002

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implicated in the mechanism of Cr(VI)-induced genotoxicity

and carcinogenicity [25,26].
Citric acid (2-hydroxy-propane-1,2,3-tricarboxylic acid,
Cit) is a model compound of several natural systems due to
its presence in plants and soils, and also a frequent domestic and
industrial chelating agent, used in the food industry and in
detergents [11].
In the present paper, we analyze the influence of the addition
of citric acid to the Cr(VI) photocatalytic system. Some features
of the system have been reported in previous papers
[11,13,21,27], but a more profound study of the system
appears to be necessary to provide explanations for solar-light
promoted processes in aquatic environments and for the use of
photocatalysis as wastewater treatment in the case of combined
mixtures.
2. Experimental
2.1. Materials and methods
Degussa P-25 was a commercial sample supplied by
Degussa AG, Germany, and used as provided. K2Cr2O7 (Carlo
Erba or Merck), citric acid (C6H8O7H2O, Riedel de Haen),
2,2,6,6-tetramethylpiperidine-1-oxyl, TEMPO (Aldrich) and
all other chemicals were of analytical reagent grade. Water was
purified with a Millipore Milli Q equipment (resistivity = 18 MV cm).
2.2. Photocatalytic runs
Photocatalytic irradiations were carried out in a recirculating reactor equipped with a quartz immersion well, 160 mm
length, 61.3 mm i.d., where a 125 W medium pressure mercury
lamp was placed. The lamp emitted predominantly at 365
366 nm with smaller emissions at lower wavelengths and with
a significant emission in the visible region. A double-walled
quartz jacket filled with water, interposed between the lamp
and the well, allowed refrigeration and filtration of IR
radiation. The TiO2 suspension (500 mL) was continuously
recirculated (2 L min1) to the photoreactor from a glass
reservoir by means of a peristaltic pump. Air was bubbled at
1 L min1 into the reservoir, which served also to take samples
for analysis and to control pH. The irradiated volume in the
well was 285 mL. The whole setup was thermostatted at 298 K.
The total incident photon flux, P0, determined by potassium
ferrioxalate actinometry [28], was 3.3  105 einstein s1,
using the same conditions of flow rate and volume as in the
experiments.
In all runs, 1 g of the catalyst was suspended in 800 mL of
Milli Q water, with the addition of some drops of 1 M
perchloric acid to reduce the agglomeration, and the suspension
was ultrasonicated for 4 min. Then, 118 mg of K2Cr2O7 and the
corresponding amount of solid citric acid to give the desired
final concentration were added to the suspension, adjusting pH
to 2 with diluted HClO4. The suspension was diluted to 1 L with
water, giving a final Cr2O72 concentration of 0.4 mM (0.8 mM
Cr(VI)). Prior to irradiation, suspensions were recirculated in

the dark at 298 K for 30 min to ensure substratesurface

equilibration. The concentration of Cr(VI) after equilibration
was taken as the initial concentration, to discount changes in the
dark (which varied between 0 and 7% in the explored
conditions). Changes after prolonged stirring (6080 min) gave
similar results and then dark reaction during the photocatalytic
runs was considered negligible. Reactions under irradiation in
the absence of TiO2 yielded also negligible Cr(VI) transformation (see later, Fig. 3 for the case R = 5). At least two
photocatalytic runs were carried out for each condition,
averaging the results.
During irradiation, 1 mL samples were periodically withdrawn, filtered through 0.2 mm cellulose acetate filters and
diluted to 10 mL for quantitative analysis. Changes in Cr(VI)
concentration were followed by UV spectroscopy at 352 nm
[29] or by the spectrophotometric method of the diphenylcarbazide at 540 nm [30]. Both techniques gave similar results,
indicating no presence of Cr(V). UVvis absorption measurements were performed employing a Hewlett-Packard diode
array UVvis, model HP 8453 A or a UV2101 Shimadzu
spectrophotometer. TOC was measured with a Shimadzu 5000A TOC analyzer in the NPOC (non-purgeable organic carbon)
mode.
2.3. Detection of intermediates by EPR spectrometry
EPR spectra were obtained at 298 K using a Bruker ER 200
X-band spectrometer (Bruker Analystische Messtechnik
GMBH, Germany). TEMPO (g = 2.0051) was used as a
concentration standard and as a standard for determination of g
factors, as recommended elsewhere [31,32]. Typical instrumental conditions were: central field, 3480 G; sweep width,
100 G; scans 120; microwave power, 43 mW; modulation
frequency, 100 kHz; time constant, 150 ms; sweep time, 1
5 s; modulation amplitude, 1.25 Gpp; receiver gain, 1  105.
Appropriate volumes of stock solutions of 1 mM K2Cr2O7
and 40 mM citric acid were added to 0.1 g L1 aqueous TiO2
suspensions previously sonicated for 5 min, and pH was
adjusted to 2 with diluted HClO4. Samples were stirred in
the dark for 10 min and then irradiated in a quartz
thin cylindrical tube inside the EPR cavity, with a 400 W,
medium pressure metal halide lamp (Phillips, HPA 400),
emitting light predominantly between 300 and 450 nm. The
output passed successively through a 10 cm water IR
filter and a long-pass glass filter, in order to isolate l 
340 nm. For this setup, we determined an incident photon
flux of 5  109 einstein s1 cm2 using ferrioxalate as actinometer [28]. In some experiments, a combination of fine
mesh metal screens of different transmittance was used to
attenuate the photon flux, rendering a value of 1  109
einstein s1 cm2.
EPR amplitude signals were transformed in radical
concentrations by comparing the area under the EPR
first derivative spectrum of the sample with that of a
standard aqueous solution of TEMPO, recorded at the same
microwave power, modulation amplitude and amplification
gain.

Please cite this article as: Jorge M. Meichtry et al., Heterogeneous photocatalysis of Cr(VI) in the presence of citric acid over TiO2 particles:
Relevance of Cr(V)citrate complexes, Applied Catalysis B: Environmental (2006), doi:10.1016/j.apcatb.2006.09.002

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3. Results and discussion

3.1. Chromium(VI) decay
Curves (a) and (b) in Fig. 1 show the time profiles of Cr(VI)
decay during the irradiation of 1 g L1 aqueous TiO2
suspensions containing 0.8 mM Cr(VI) in the absence and in
the presence of 2 mM citric acid (pH 2, continuous air
bubbling). At this concentration and pH (which did not vary
during the photocatalytic run), the main Cr(VI) species is
HCrO4 [33]. In the absence of citric acid, the reaction arrives
to an arrest, ascribed to a short-circuiting due to the continuous
reduction and reoxidation of chromium species by holes or
hydroxyl radicals (Eq. (5)); this short-circuiting can be
suppressed by the addition of a strongly competing chelating
(sacrificial) species D (Eq. (6)). In a simplified way:
CrVI ecb  ! CrV

(1)

CrV ecb  ! CrIV

(2)

CrIV ecb ! CrIII

(3)

H2 O hvb ! HO H

(4)

103

we noticed a five-fold enhancement of the initial rate of Cr(VI)

reduction. It should be stressed that Cr(III) was invariably found
in the spectra of the filtered solution at long irradiation times.
Fig. 2 shows the spectra of the filtered solutions of the
photocatalytic experiment at t = 0 and after 60 min of irradiation
in the 400600 nm range. The peak around 575 nm can be
assigned to the absorption of the Cr(III)Cit complex [34], and
this is confirmed by the comparison with the spectrum of a
solution prepared with 0.45 mM Cr(III) and excess citric acid at
pH 2, which roughly coincides in the 450600 nm range. The fact
that the observed absorption is lower than that expected if all
initial Cr(VI) would have been transformed to Cr(III)Cit
(0.8 mM) can be attributed to two main reasons: (1) degradation
of Cit and formation a less absorbing Cr(III) species with
oxoglutaric acid or some other intermediate of citric acid
degradation, this substantiated by a peak at 290 nm (Fig. 2(b)), in
agreement with the conclusions of Hug and Laubscher [39] for a
similar system (photoinduced Cr(VI) reduction by Fe(III) in the
presence of citrate); (2) adsorption of Cr(III) onto the TiO2

CrV=CrIV=CrIII hvb HO

! CrVI=CrV=CrIVHO
D hvb ! D

(5)
(6)

In our case, D is citric acid, which, besides suppressing the

short-circuiting, forms a very stable complex with Cr(V) [34
38]:
Cit hvb ! Cit

(7)

CrV Cit ! CrVCit

(8)

Similarly to our previous findings with oxalate and EDTA,

citric acid addition favors chromium(VI) elimination. For the
conditions in Fig. 1 (i.e., initial Cit/Cr(VI) molar ratio R = 2.5),

Fig. 1. Cr(VI) evolution with time under continuous irradiation of 1 g L1

aqueous TiO2 aerated suspensions containing initially 0.4 mM K2Cr2O7
(0.8 mM Cr(VI)) (a) in the absence and (b) in the presence of 2 mM citric
acid at pH 2. Curve (c): TOC decrease for the experiment containing citric acid.
Curve (d): TOC decrease for the experiment containing citric acid in the
absence of Cr(VI). Total incident photon flux, P0 = 3.3  105 einstein s1.

Fig. 2. (a) Spectra at t = 0 and after 60 min under continuous UV irradiation of

1 g L1 aqueous TiO2 aerated suspensions containing initially 0.4 mM K2Cr2O7
(0.8 mM Cr(VI)) and 1 mM citric acid at pH 2 in the 400600 nm range. The
spectrum of a solution containing 0.45 mM Cr(NO3)3 and 1.125 mM citric acid,
pH 2 is also shown. (b) Same in the 250350 nm range. Total incident photon
flux, P0 = 3.3  105 einstein s1.

Please cite this article as: Jorge M. Meichtry et al., Heterogeneous photocatalysis of Cr(VI) in the presence of citric acid over TiO2 particles:
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surface, evidenced by a greenish color on the catalyst surface

after irradiation [19].
TOC evolution in the absence (curve (d)) and the presence
(curve (c)) of Cr(VI) is also shown in Fig. 1. It is interesting to
observe that TOC decrease is higher in the presence of the metal
in the first stages (cf. 15% with 10% at 20 min in both
conditions), but at longer irradiation times (120 min) there is an
inhibition in TOC degradation. We propose that this may reflect
the deactivation of the photocatalyst attributed to Cr(III)
adsorption.
We reasoned that higher initial citric acid/Cr(VI) molar
ratios, R, would always favor Cr(VI) depletion, eventually
reaching a saturation limit, after which a further addition of the
donor would be meaningless. However, as shown in Fig. 3, we
found that increasing R above 1.25 was detrimental. This
behavior has been observed in other systems, e.g., Cr(VI) plus
salicylic acid [11,12] but not completely analyzed. Table 1
summarizes these results by giving the initial apparent pseudofirst-order rate constants, calculated from the plots, as a
function of R. However, rates were always higher than in the
absence of citric acid.
In an attempt to rationalize the above findings, the evolution
of the primary intermediate, Cr(V) species, was analyzed. In
homogeneous systems, the formation of chromium(V) complexes with citric acid has been previously observed by UV [34]
and EPR spectroscopy [37,36]. Although the structure of
citrate, a 2-hydroxycarboxylato ligand, makes the Cr(V)Cit
complexes quite stable [38], and their detection by UVvis
spectroscopy has been reported (absorption at l = 350 nm,
e 2000 M1 cm1 [34]), they cannot be easily detected in
complex reaction mixtures. Conversely, Cr(V)Cit can be
readily observed by EPR spectroscopy due to the specificity of
the technique and its high sensitivity. Fig. 4 shows the spectrum
obtained in a typical experiment performed under irradiation of
a 0.1 g L1 TiO2 suspension containing initially 0.4 mM
K2Cr2O7 (0.8 mM Cr(VI)) and 4 mM citric acid at pH 2 in
the cavity of the EPR spectrometer. The signal is centered at

Table 1
Initial apparent pseudo-first-order rates for Cr(VI) reduction at different citric
acid concentrations ([Cr2O7K2]0 = 0.4 mM, 0.8 mM Cr(VI))
Citric acid (mM)

k0 (104 s1)

0
0.1
0.4
1
2
4
10
40

0
0.125
0.5
1.25
2.5
5
12.5
50

6.0
18.7
26.3
31.4
27.4
23.8
21.4
15.4

Conditions as in Fig. 1, R: initial citric acid/Cr(VI) molar ratios.

giso = 1.977 with four 53Cr hyperfine satellites (coupling

constants 18.7 G). The spectra is almost identical to that
reported in the above references and has been ascribed to
CrO(CitH2)2.
Irradiation experiments of TiO2 suspensions in the EPR
cavity in the same conditions as before but with variable citric
acid concentration were performed in order to obtain the time
profiles of the Cr(V)Cit complex. In this case, the field was
fixed at g = 1.977 to follow the evolution of the signal
amplitude. A small paramagnetic signal of Cr(V)Cit complexes appeared immediately after mixing the solutions, either
in the presence or in the absence of TiO2. It is worthwhile to say
that we carefully checked that the initial amplitude remained
constant in the dark and even under irradiation in the absence of
the semiconductor, in the time range of the EPR experiments
(typically 1020 min). The high sensibility of the EPR
technique allows us to determine initial rates of Cr(V)Cit
formation at low, negligible Cr(VI) conversion (i.e., without the
influence of secondary steps or intermediates). Fig. 5 shows that
the time evolution of chromium(V) species is nearly
independent of Cit above R  1.25. These observations could
simply reflect the fact that the trapping of chromium(V) species
is not kinetically controlled and that the increase of Cit
concentration above 1 mM (R = 1.25) does not modify the
initial rate of Cr(V) formation (Cr(VI) reduction). Thus, the
observations in Fig. 3, i.e., the inhibition at high R values,
should be ascribed to some secondary step, for example the
competition between Cr(V)Cit complexes and Cr(VI) for
conduction band electrons at higher conversions (reactions (1)
and (9)):
CrVCit ecb  ! CrIV

Fig. 3. Cr(VI) evolution with time under continuous UV irradiation of 1 g L1

aqueous TiO2 aerated suspensions containing initially 0.4 mM K2Cr2O7
(0.8 mM Cr(VI)) and several citric acid concentrations. R: initial citric acid/
Cr(VI) molar ratios. Total incident photon flux, P0 = 3.3  105 einstein s1.

(9)

or to the competition of Cr(V)Cit and Cit for holes (reactions

(7) and (5)). Further work on this issue is in progress.
In the experiments carried out in the recirculating reactor
(Fig. 1), we proposed that the amount of Cr(V) and Cr(IV) was
very low, a result different from that obtained for Cr(V) during
the EPR experiments shown in Fig. 5. It is noteworthy to
remember that the irradiation intensity was much higher in the
experiments of Fig. 1 and that the experiments in Fig. 5 involve
negligible Cr(VI) conversion.
We performed a set of EPR experiments with lower
chromium concentrations and the higher photon flux attainable
in this setup in order to observe the time evolution of the

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105

Fig. 4. EPR spectra of the Cr(V)Cit complex formed under continuous UV irradiation of a 0.1 g L1 TiO2 aerated suspension at pH 2. Conditions: [citric
acid] = 4 mM, [K2Cr2O7] = 0.4 mM (0.8 mM Cr(VI)). Central field: 3483 G, modulation amplitude: 1.25 Gpp, gain: 1.25  105. The inset shows the structure of the
complex proposed in Ref. [36]. Incident photon flux = 5  109 einstein s1 cm2.

complex at measurable Cr(VI) conversions, and to quantify the

relevance of Cr(V)Cit complexes in the mechanism. Fig. 6
shows the results of an irradiation experiment of a TiO2
suspension (0.1 g L1, 50.5 mM initial K2Cr2O7 = 101 mM
Cr(VI), R = 5, pH 2). Curve (a) shows the profile obtained under
continuous irradiation, while curve (b) describes the behavior
observed in a separate irradiation experiment in which the light
was turned off when the signal was at its maximum. The
persistence of the signal in the dark is consistent with the high
stability of the complex. Spectrophotometric measurements

indicated that, after 2 min of irradiation, 40% of Cr(VI) was

reduced, which corresponds to 40.4 mM. Thus, the amount of
complex at the maximum represents nearly a 15% of Cr(VI)
losses, indicating that an important fraction of chromium
reduction occurs through the Cr(V)citrate complex. This result
sharply differs from our previous findings with oxalic acid or
EDTA, where only a small amount of complexes was detected
[2,24].
To reinforce our conclusions, a comparison of the oxalic acid
and citric acid systems under similar conditions (0.1 g L1

Fig. 5. Time dependence of [Cr(V)Cit] obtained under continuous UV

irradiation conditions of a 0.1 g L1 aqueous TiO2 suspension containing
initially 0.4 mM K2Cr2O7 (0.8 mM Cr(VI)), pH 2 and variable citric acid
concentrations. R: initial citric acid/Cr(VI) molar ratios. Incident photon
flux = 1  109 einstein s1 cm2.

Fig. 6. Time dependence of [Cr(V)Cit]. Curve (a): profile obtained under

continuous UV irradiation of a 0.1 g L1 aqueous TiO2 suspension containing
initially 50.5 mM K2Cr2O7 (101 mM Cr(VI)) and 0.5 mM citric acid, R = 5, pH
2. Incident photon flux = 5  109 einstein s1 cm2. Curve (b): same as (a)
but light was turned off when the signal was at its maximum.

Please cite this article as: Jorge M. Meichtry et al., Heterogeneous photocatalysis of Cr(VI) in the presence of citric acid over TiO2 particles:
Relevance of Cr(V)citrate complexes, Applied Catalysis B: Environmental (2006), doi:10.1016/j.apcatb.2006.09.002

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Fig. 7. Comparison of [Cr(V)Ox] and [Cr(V)Cit] generation under continuous irradiation of a 0.1 g L1 TiO2 aerated suspension. Initial conditions: [citric acid] or
[oxalic acid] = 1 mM, [K2Cr2O7] = 0.2 mM (0.4 mM Cr(VI)), pH 1.5, T = 298 K. Incident photon flux = 1  109 einstein s1 cm2.

TiO2, 1 mM citric acid or oxalic acid, 0.4 mM Cr(VI), pH 1.5)

was performed. pH 1.5 was chosen due to the instability of
Cr(V)oxalate at higher pH [2]. The time evolution of both
Cr(V)L complexes is shown in Fig. 7. It is apparent that a
much higher amount of Cr(V) is accumulated in the presence of
citric acid either under irradiation or in the dark (t = 0). It is
worthwhile to notice that the monotonous increase of Cr(V)
Cit complexes observed in Fig. 7 is a mere consequence of their
rate of formation being much higher than their rate of
destruction in the conditions of these EPR experiments, which
involve very low Cr(VI) conversions. However, the differences
observed in curves (a) and (b) of Fig. 6 clearly indicate that the
removal of the citrate complex is indeed feasible upon
irradiation in the photocatalytic system.
4. Conclusions
Addition of excess citric acid facilitates Cr(VI) TiO2
photocatalytic reduction in comparison with the same system in
the absence of the donor. This synergy helps the reaction by
hindering the electron-shuttle mechanism that occurs in pure
water. The rate of hexavalent chromium transformation is a
function of the amount of citric acid present in the medium: the
maximum rate was attained for an initial Cit/Cr(VI) molar ratio
equal to 1.25. Higher citric acid amounts are detrimental, but
the efficiency is always better than in pure water.
According to EPR experimental evidences, Cr(VI) reduction
is initiated by an one-electron process forming Cr(V), which in
the presence of citric acid is readily trapped as the very stable
CrO(CitH2)2 species. Quantitative EPR determinations
indicate that an important fraction (nearly 15%) of the reduced
Cr(VI) could be detected as Cr(V)Cit during the course of an
irradiation experiment. The photocatalytic decomposition of
Cr(V)Cit was ascertained by interrupting the light after a

certain fraction of the complex was formed and observing that

the amplitude of the paramagnetic signal was constant, at
variance with the results obtained under continuous irradiation.
Based on the fact that above R = 1.25 Cr(V)Cit formation
rates at extremely low conversions are nearly independent of
citric acid concentration, we proposed that the detrimental
effect determined at higher conversions (for R > 1.25) should
be ascribed to secondary steps, i.e., the competition for
conduction band electrons between Cr(VI) and Cr(V) complexes or to the competition of Cr(V)Cit and Cit for holes.
Because of the stability of the complex, a large fraction of the
reduced Cr(VI) accumulates in this form, a fact different from
that observed with EDTA or oxalate.
The distinctive behavior of the Cr(VI)/citric acid photocatalytic system here reported in contrast with others could
explain processes in natural waters. The possibility of the
formation of very stable and carcinogenic Cr(V)Cit complexes should be taken into account when using TiO2
photocatalysis for remediation of systems containing simultaneously Cr(VI) and citric acid. However, this paper evidences
that, although the persistence of Cr(V)Cit may be long and it
should be continuously evaluated during the treatment, it finally
photocatalytically decays, ending in less noxious Cr(III)
species.
Acknowledgements
This work was performed as part of Comision Nacional de
Energa Atomica P5-PID-36-4 Program, CONICET/CNRS
grant for cooperation between Clermont Ferrand and Argentine
laboratories, Agencia Nacional de la Promocion de la Ciencia y
la Tecnologa, PICT03-13-13261 and PICTO 02-006-11307.
MIL and MAG are members of CONICET. JMM thanks
CONICET for a doctoral fellowship.

Please cite this article as: Jorge M. Meichtry et al., Heterogeneous photocatalysis of Cr(VI) in the presence of citric acid over TiO2 particles:
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Please cite this article as: Jorge M. Meichtry et al., Heterogeneous photocatalysis of Cr(VI) in the presence of citric acid over TiO2 particles:
Relevance of Cr(V)citrate complexes, Applied Catalysis B: Environmental (2006), doi:10.1016/j.apcatb.2006.09.002