Environ. Sci. Technol.

2009, 43, 8361–8366

conditions, so it would be ideal for use in clean technology.

Mechanism Investigation of Visible However, slow reaction rate and poor solar efficiency has
Light-Induced Degradation in a hindered its commercialization (10). To handle these prob-
lems, many attempts by researchers have been carried out
Heterogeneous TiO2/Eosin to modify its surface or bulk properties such as doping with
various metal ions or nonmetals (11-13), deposition of noble
Y/Rhodamine B System metals (14, 15), and mixing of two semiconductors (16-18).
Dye sensitization is another method to eliminate these
M I N G C A I Y I N , †,‡,§,| Z H A O S H E N G L I , †,§ drawbacks, and until previously, various types of dyes have
J I A H U I K O U , †,‡,§ A N D Z H I G A N G Z O U †,‡,§,* been used (19-28). For example, TiO2 particles sensitized by
Eco-materials and Renewable Energy Research Center (ERERC), RuII [bpy-(COOH)2]32+ have demonstrated good performance
Nanjing University, Nanjing 210093, P. R. China, Department of (29). Furthermore, a lot of research on photocatalytic
Physics, Nanjing University, Nanjing 210093, P. R. China, decomposition of colored or colorless organic pollutants has
National Laboratory of Solid State Microstructures, Nanjing been done. The mechanism of dye-sensitized photodegra-
University, Nanjing 210093, P. R. China, and Department of dation of organic pollutants over TiO2 is generally regarded
Chemistry, Zhengzhou University, Zhengzhou 450052, P. R. China as follows: the dyes, rather than the TiO2 photocatalyst, are
subject to visible light excitation. The excited dye molecules
Received July 6, 2009. Revised manuscript received August subsequently transfer electrons onto conduction bands (CBs)
24, 2009. Accepted September 9, 2009. of TiO2, leading to formation of dye cationic radicals. The
injected electrons then react with the dioxygen adsorbed on
the surface of TiO2 and generate a series of active oxygen
species such as O2•-, H2O2, and •OH (30), i.e., the CB of TiO2
Visible light-induced degradation of rhodamine B (RhB) and acts only as a mediator for transferring electrons from the
eosin Y (EO) in a heterogeneous TiO2 P-25/EO/RhB system was sensitizer to substrate electron acceptors on the TiO2 surface,
investigated in the present work. The results showed that and the valence band (VB) remains unaffected.
the photodegradation of RhB is enhanced significantly when Although the basic processes for dye-sensitized photo-
EO is introduced into the P-25/RhB system. Under optimal degradation of organic pollutants has been extensively
conditions (50 mg P-25, 20 mg L-1 EO), RhB (4 mg L-1) almost reported, the synergistic mechanism of two dye pollutants
applied to a heterogeneous TiO2 system remains unclear until
decomposed completely after 35 min of visible light irradiation,
now, even if it exists extensively in dye wastewater effluents.
though EO was photodegraded simultaneously. The possible It is conceivable that the degradation process of two dyes
photodegradation mechanism was studied by the examination system will be more complex compared with that of single
of active species HO•, O2•- anions, or dye radical cations dye because organic dye often serves as a sensitizer and
through adding their scavengers such as methanol, t-butanol, substrate to be degraded (31, 32). In addition, in the field of
benzoquinone, EDTA, and the I- anion. In addition, the photocatalysis, there have been many debates as to whether
electron paramagnetic resonance (EPR) spin trapping technique photoreactions occur on the catalyst surface involving
was also used to monitor the active oxygen species formed reactions with positive holes (hvb+) or surface-bound •OH or
in the photocatalytic process. Combined with the contrastive in the solution with free radicals (33, 34).
experiments under different atmospheres (N2-purged or air) and All of the above background information led us to
in different systems, it can be deduced that dissolved O2 investigate the photodegradation of two dyes in a hetero-
plays a crucial role in dye photodegradation and the O2•- anion geneous TiO2 P-25 system, and two xanthene dyes, eosin Y
(EO) and rhodamine B (RhB), were used as the model
is possibly the major active oxygen species. The low
compounds in the present study. Their structures are
degradation rate with the introduction of EDTA or I- indicated presented as Figure 1.
that dye radical cations also play a part in photodegradation.
Compared with EO, RhB, which contains four N-ethyl
Furthermore, except for the dye-sensitized photodegradation on groups at either side of the xanthene ring, is relatively stable
the P-25 surface, reaction in bulk solution also occurs in this in aqueous solutions upon visible light irradiation (35),
system, leading to effective photodegradation of RhB. probably due to the different substituent groups on the
xanthene ring (36). The main purpose of this work is to
Introduction examine the optimal experimental conditions with the highest
Photocatalysis has many merits in terms of the removal of photodegradation efficiency and investigate the degradation
harmful organic compounds, wastewater treatment, and mechanism of this complex system. The investigation of this
clean up of polluted air (1-4). Semiconductor photocatalysts, system would set a foundation for treating dye pollutants in
for example, TiO2 (5-9), have gained much attention because wastewater effluents.
they can potentially utilize inexpensive and inexhaustible
solar radiation. In addition, TiO2 is nontoxic, inexpensive,
and more stable than other photocatalysts under ambient

* Corresponding author phone: +86-25-83686630; fax: +86-25-

83686632; e-mail: zgzou@[Link].
†
Eco-materials and Renewable Energy Research Center (ERERC),
Nanjing University.
‡
Department of Physics, Nanjing University.
§
National Laboratory of Solid State Microstructures, Nanjing
University.
|
Zhengzhou University. FIGURE 1. Molecular structures of eosin Y and rhodamine B.
10.1021/es902011h CCC: $40.75  2009 American Chemical Society VOL. 43, NO. 21, 2009 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 8361
Published on Web 09/30/2009
FIGURE 2. (a) Time courses of dye concentration during photodegradation with different EO concentrations (Note: all C/Co values
were obtained only by the maximum absorption in the whole absorption spectrum in order to evaluate the degradation efficiency of
both dyes). (b) Time courses of EO and RhB concentrations during photodegradation with 20 and 25 mg L-1 of EO.

Experimental Section experiments, and the gas was purged during the whole
Materials and Measurements. TiO2 P-25 (a mixture of 80% experiment.
anatase and 20% rutile with an average specific surface area
of about 50 m2/g) was obtained from Degussa Co. of Germany. Results and Discussion
Mesoporous TiO2 was prepared in our lab according to the Effect of EO and Catalyst Concentration on Dye Photo-
literature method (37). Commercial TiO2, EO, RhB, and degradation. It is well-known that dye photodegradation
methyl orange (MO) were obtained from Sinopharm Chemi- rate is affected by many factors such as light source, catalyst
cal Reagent Co., Ltd., and used as received. Stock solutions amount, and dye concentration (38), so the optimal degra-
of EO (1 g L-1), RhB (500 mg L-1), and MO (500 mg L-1) were dation conditions, EO and catalyst concentration, were
prepared by dissolving certain amount of dyes in deionized investigated at first.
water. The deionized water used was ultrapure (18 MΩ cm) The concentration of RhB was fixed to 4 mg L-1, and the
and prepared by a Barnstead purification system. 5,5- catalyst amount was 50 mg in the initial experiment, while
Dimethyl-1-pyrroline N-oxide (DMPO) was purchased from the concentration of EO was varied from 10, 15, 20, to 25 mg
Tokyo Chemical Industry Co., Ltd. All other chemicals were L-1. From the degradation courses illustrated in Figure 2a,
of reagent grade and used without further treatments. The it is shown that photocatalytic activity is enhanced gradually
specific surface areas were measured with Micrometrics Tri- with an increasing proportion of EO, and optimal photo-
Star 3000 surface area and porosity analyzer by the catalytic efficiency is obtained at a 5:1 molar ratio, in which
Brunauer-Emmett-Teller (BET) method. the EO concentration is 20 mg L-1, and the two dyes are
The detailed mechanism of the photocatalytic dye deg- almost 100% decolorized in about 35 min. It is worthwhile
radation in neutral solution was elucidated through the use to note that the C/C0 values in Figure 2a were obtained only
of different hvb+ or •OH, O2•- scavengers and EPR tests. EPR through maximum absorption in order to evaluate the
spectra were detected using a Bruker EMX-10/12 electron degradation efficiency of both dyes. The time courses of RhB
paramagnetic resonance spectrometer. The settings for the concentration during photodegradation are supplied in
EPR spectrometer were center field, 3480.0 G; sweep width, Figure S1of the Supporting Information.
200.0 G; microwave frequency, 9.751 GHz; and power, 19.873 However, the degradation rates of the two dyes decreased
mW. The light source for EPR determination was a 300 W again with a further increase in EO concentration (Figure
xenon lamp equipped with a 420 nm cutoff filter. The three- 2b), probably due to the competitive adsorption of EO and
dimensional (3D) fluorescence spectra of EO/RhB aqueous RhB on the P-25 surface. The adsorption determination
solutions were recorded on a Varian Cary Eclipse fluorescence results indicated that the adsorption amount of EO decreased,
spectrophotometer. whereas that of RhB increased when the concentration of
Photocatalytic Experiments. The concentration of RhB EO was enhanced from 20 to 25 mg L-1. Probably it is just
(or MO) was fixed to 4 mg L-1 for all experiments, and the this reduction in the EO amount on the P-25 surface that
concentration of EO varied from 10 to 25 mg L-1 under leads to the lower degradation rate of RhB. However, this
different conditions. A 300 W Xe lamp equipped with a 420 phenomenon can also be elucidated as follows. If dye
nm cutoff filter was used as a light source. The aqueous concentration increases continuously, the dissociative dye
suspension (100 mL) of a certain amount of EO and RhB (or molecules, which cannot participate in electron transfer on
MO) and 50 mg of photocatalyst was placed in a vessel. Prior the catalyst surface but absorb a part of incident light at the
to irradiation, the suspension was magnetically stirred in same time, will also increase and result in the loss of part of
the dark for about 30 min to establish an adsorption- the incident light by acting as an internal filter, resulting in
desorption equilibrium. The reactor was open to air (or a decrease in the degradation rate (38).
purged with gases), and the suspension was stirred magneti- In order to investigate the influence of catalyst concen-
cally during the irradiation. At regular time intervals, an tration on dye degradation, 30, 50, 60, or 80 mg P-25 was
aliquot of 3-4 mL was withdrawn and filtered through a 0.45 used for the P-25/EO/RhB system, and the degradation
µm syringe filter to remove the particles. During the courses are shown in Figure 3a. It can be found that when
experimental procedure, changes in the concentration of 50 mg P-25 was used, optimal decolorization efficiency was
two dyes were monitored from its characteristic absorption obtained. The UV-vis spectra of the aqueous samples
band (generally 516 nm for EO and 553 nm for RhB) using collected at various irradiation time intervals for 50 mg P-25
a Cary 50 Probe UV-vis spectrophotometer. The amount of are shown in Figure 3b. In Figure 3a, during the first 10 min,
the dyes adsorbed on TiO2 was calculated from the absor- the optimal decolorization efficiency observed with TiO2 of
bance difference (∆A ) Amix - Aeq). 80 mg is probably due to the higher dosage of TiO2 leading
The purging N2 or O2 experiment was conducted at a to more dye molecules being adsorbed on the surface of
flow rate of ∼0.08 L min-1 for 30 min prior to the TiO2.

8362 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 43, NO. 21, 2009
FIGURE 3. (a) Time courses of dye concentration during photodegradation with different amounts of P-25 in the P-25/EO/RhB system.
(b) Temporal UV-visible absorption spectra observed for the P-25/EO/RhB system as a function of irradiation time (EO, 20 mg L-1;
RhB, 4 mg L-1).

It is well-known that photodegradation of RhB usually

occurs via two competitive processes: (1) N-deethylation and
destruction of the conjugated structure and (2) a hypso-
chromic shift of the absorption band presumed to result
from the formation of a series of N-deethylated intermediates
in a stepwise manner, which often exists (39, 40). However,
no obvious absorption band shift was observed in the present
system (P-25, 50 mg; RhB, 4 mg L-1; and EO, 20 mg L-1),
suggesting the efficient decomposition of the conjugated
xanthene ring in RhB (40, 41). However, when the EO
concentration decreased to 10 mg L-1, a distinct hypso-
chromic shift emerged (Figure S2 of the Supporting Infor-
mation). Form Figure 3b, it is shown that not only the main
absorbance in the visible region but also the peaks in the UV
region are reduced with irradiation, indicating that the dye
chromophores and aromatic ring were destroyed, in other
words, the dye molecules were degraded instead of being
only decolorized (40). FIGURE 4. Time courses of dye concentration during
photodegradation in different systems (Note: all C/Co values
Photodegradation Mechanism were obtained only by the maximum absorption in the whole
Photodegradation on a P-25 Surface and/or in Bulk absorption spectrum in order to evaluate the degradation
Solution. From Figure 2, it is also shown that the introduction efficiency of both dyes).
of EO has a great influence on the photocatalytic degradation point of view, the electron transfer from the excited RhB to
of RhB, though EO decomposed simultaneously. In order to EO should also be possible; however, the degradation rate
make the photodegradation process clear, a series of of RhB is improved, on the contrary. This can be explained
contrastive experiments were conducted. from the experimental fact that EO is more easily degraded
No degradation was detected in the dark in the system than RhB under visible light irradiation, which implies that
of EO/RhB or that of P-25/EO/RhB, signifying that the dye in an EO system, dye radical cations, 1O2 and O2•-, are more
degradation in the present study is indeed through a liable to form than in a RhB system. That is to say, more
photocatalytic process. However, in the absence of P-25, active species exist in an EO/RhB system than in a single
simultaneous degradation of EO and RhB was observed in RhB system, and accordingly, the photodegradation rate of
a homogeneous EO/RhB system under visible light irradia- RhB was increased greatly.
tion, and the degradation rate of RhB increased greatly A series of experiments were also conducted in order to
compared with a single RhB system (Figures 4 and 5), though clarify the case for a heterogeneous TiO2/EO/RhB system.
that of EO decreased to a certain extent. The results showed that TiO2-mediated dye photodegradation
To the best of our knowledge, the probable pathway for proceeds and plays a major role because the degradation
homogeneous dye photodegradation in the presence of rate of the heterogeneous systems were much larger than
dissolved oxygen is homolysis of excited dyes into radicals that of the homogeneous ones, for example, P-25/RhB .
or electron transfer from excited dye molecules to electron RhB, P-25/EO > EO, and P-25/EO/RhB . EO/RhB as depicted
donor (for example, O2) to form dye radical cations, which in Figure 4. So, electron transfer from EO or RhB to the CB
are decomposed subsequently by a superoxide radical anion of TiO2 occurs and plays an important role in dye photo-
(O2-•) or singlet oxygen (1O2) (42). So, for the EO/RhB degradation, which can also be testified by the oxidation
homogeneous system, self-photolysis and mutual interaction potentials of excited dyes (-1.53 and -1.42 V vs NHE, pH
between two dyes (direct electron transfer between EO and 7 for the excited singlet states of EO and RhB, respectively)
RhB) may both occur (43, 44), verified by their redox potentials and that of CB of TiO2 (-0.52 V vs NHE, pH 7) (46). However,
(E0 (EO*/EO+) ) -1.53 V, E0 (EO/EO+) ) 0.80 V, E0 (RhB*/ it also shows that the electron transfer from EO to the CB of
RhB+) ) -1.42 V, E0 (RhB/RhB+) ) 0.95 V vs NHE, pH 7) (45) P-25 should be easier than that for RhB, consistent with the
and that of O2 (E0 (O2/O2•-) ) -0.28 V vs NHE, pH 7) (46), results that EO is more liable to be degraded than RhB.
and from which it can also be concluded that RhB plays the Furthermore, it should be noted that high temperature
role of stabilizer (47), namely, acting as an electron donor might promote thermal decomposition of dyes. So, a dark
sacrificial agent of EO in the degradation course. From this control in 40 °C proceeded, and the result showed no

VOL. 43, NO. 21, 2009 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 8363
FIGURE 5. The EO and RhB degradation courses for EO/RhB homogeneous system (a) and heterogeneous P-25/EO/RhB system (b)
under air and N2-purged atmospheres, respectively (a: EO, 20 mg · L-1; RhB, 4 mg · L-1; b: EO, 10 mg · L-1; RhB, 4 mg · L-1).
degradation took place after 120 min, indicating that thermal
decomposition was negligible in a P-25/EO/RhB system.
Effect of Photodegradation Atmosphere. Comparison
of the photolysis in air equilibrium (no gas purged), N2-
purged, and O2-purged conditions was also undertaken to
further elucidate the degradation mechanism, and some
degradation courses are shown in Figure 5.
For the dye self-photodegradation of a EO/RhB system,
it is worthwhile to note that the degradation rates of EO and
RhB under air equilibrium conditions are clearly higher than
those under N2-purged condition (Figure 5a). In addition,
under a N2 atmosphere, the RhB decolorization rate for a
EO/RhB system is still higher than that for a single RhB system,
indicating that except for the photolysis process, interaction
between two dyes in the bulk solution also plays an important
role in degradation, consistent with the results obtained
above. Another separate experiment showed that additional
O2 purging does not result in a further increase in the FIGURE 6. EPR spectra of DMPO-•OH adducts after different
degradation rate, illustrating that air-equilibrated dissolved periods of irradiation for P-25/RhB dispersion in H2O.
oxygen was sufficient for dye degradation.
However, from Figure 5, it is also shown that under a N2 Electron transfers from EDTA or KI to them make the dye
atmosphere, the degradation rates of EO and RhB in a radical cations return to the ground states, and correspond-
heterogeneous P-25/EO/RhB system are higher than those ingly, result in a low degradation rate. Furthermore, the
in a homogeneous EO/RhB one, which suggests that in the influence of EDTA or I- on the degradation manifests that
anoxic condition, catalyst P-25, has an enhancing effect on the dye radical cations also play a part in the photocatalysis
the dye degradation, namely, the surface reaction is more course.
effective than that in the bulk solution, also in accordance As depicted above, dissolved O2 plays a key role in EO and
with the above results. RhB degradation, but •OH has been proven not to be the
Effect of Scavenger Agents and Investigation on Active major oxidation species in this process. So, BQ, an O2•-
Species. Another series of tests were also conducted to probe quencher, was used to examine the role of O2•- (49). The
the mechanism responsible for this visible light-induced great influence of BQ on degradation (only about 40%
photocatalysis. At first, some sacrificial agents, such as tert- degraded after 60 min; see Figure S3e of the Supporting
butanol (tBuOH) [V (tBuOH/H2O) ) 1:20], methanol [V Information) showed that the dye photodegradation is caused
(CH3OH/H2O) ) 1:4], EDTA (c ) 10 mmol L-1), KI (c ) 10 by O2•- to a large degree.
mmol L-1), and benzoquinone (BQ, c ) 1 mmol L-1) were The EO concentration increases for panels d and e of
added to the degradation system in order to ascertain the Figure S3 of the Supporting Information are probably
active species in degradation process. attributed to the changes in the surface chemistry of P-25
The results showed that when •OH scavengers, tBuOH due to the introduction of I- anions or BQ, respectively, which
(48), or methanol was put into the degradation systems, no further affect the adsorption of EO (anionic dye) and RhB
significant changes occurred on dye degradation except for (cationic dye). The partial desorption of EO from the P-25
a hypsochromic shift of the absorption band (Figure S3a,b surface possibly induced the increases in EO concentration.
of the Supporting Information), showing that the •OH is not EPR Experiments. To further confirm the active species,
the major oxidation species in this process. However, when we carried out EPR/DMPO spin trapping experiments to
holes scavenger, EDTA (48) or KI (44), was introduced, the detect the active oxygen species in this system under visible
degradation rates of EO and RhB were depressed to some light irradiation (50, 51). The results revealed that no
extent (Figure S3c,d of the Supporting Information). It is DMPO-•OH or DMPO-O2•- spin adducts were detected
well-known that no hvb+ arises on P-25 under irradiation of before irradiation, while after irradiation, characteristic peaks
visible light because its VB is unaffected, so the low of DMPO-•OH were obviously observed for the P-25/RhB/
degradation rate in the presence of EDTA or KI may be DMPO system (Figure 6), though no peaks were observed for
assigned to electron transfer between them and two dye either the P-25/EO/DMPO or P-25/EO/RhB/DMPO one. This
molecules, namely, EDTA and I- act as electron donors, which is possibly due to the intensive and fast photodegradation
can also be confirmed by their redox potentials and that of of EO, which acts as a quencher of O2•- and •OH and results
I- (E (I•/I-) ) 1.3 V (44) and E (I3-/I-) ) 0.535 V vs NHE). in a competition reaction between EO and DMPO. By

8364 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 43, NO. 21, 2009
 influence degradation, consistent with the literature reported
(54). In addition, the dye degradation over insulator Al2O3
(data not shown) exhibited a much lower degradation rate
than that without a catalyst, also indicating that the catalyst
property plays a major role in the dye photodegradation.
Photodegradation of MO. The photodegradation of MO
in heterogeneous P-25/EO/MO was also investigated, and
similar results to RhB were obtained (Figure S6 of the
Supporting Information). That is to say, introducing EO into
a P-25/MO suspension also leads to a significant improve-
ment in MO degradation.
Elimination of Likelihood of Stray UV Light. Degradation
of MO in a P-25/EO/MO system with a cutoff filter of 480 nm
was conducted in order to diminish the probability of stray
UV light. The result indicated that no obvious changes take
place in the dye photodegradation rate, which eliminates
FIGURE 7. EPR spectra of DMPO-O2•- adducts in DMSO after 5 the likelihood of stray UV light.
min irradiation: (a) P-25/RhB and (b) P-25/RhB/EO dispersion.
comparison, EO should be more active than DMPO for oxygen Acknowledgments
active species. Financial support from the National Natural Science Foun-
Moreover, for the P-25/RhB/DMPO system, the intensity dation of China (50732004 and 20773064), Science and
of DMPO-•OH increased with prolonged irradiation time Technology Research Program of the Ministry of Education
(2-5 min). However, when the irradiation time was much (MOE) of China (307012), and National Basic Research
longer (30 min), the EPR signals disappeared, similar to the Program of China (973 Program, 2007CB613301, and
literature reported (52). 2007CB613305), and China Postdoctoral Science Foundation
As reported in the literature, O2•- is unstable in aqueous (20080441028) are gratefully acknowledged.
solution and is easily decomposed into •OH, and the reaction
rate constant of DMPO with •OH is much larger than that
with O2•- (53). So, it is usual that O2•- is hard to detect, though
Supporting Information Available
Figures S1-S6. This material is available free of charge via
it is formed in the reaction. In order to further verify whether
the Internet at [Link]
O2•- is formed in the P-25/RhB/DMPO system, a polar aprotic
solvent, DMSO, was used instead of water (53), and the results
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