Journal of Power Sources 166 (2007) 74–79

Short communication

Visible-light-induced hydrogen production over Pt-Eosin Y catalysts

with high surface area silica gel as matrix
Xiaojie Zhang a,c , Zhiliang Jin a , Yuexiang Li b , Shuben Li a , Gongxuan Lu a,∗
a State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics,
The Chinese Academy of Sciences, Lanzhou 730000, PR China
b Department of Chemistry, Nanchang University, Nanjing Road 245, Nanchang, 330047, PR China
c Graduate University of the Chinese Academy of Sciences, Beijing 100101, PR China

Received 4 October 2006; received in revised form 11 December 2006; accepted 25 December 2006
Available online 16 January 2007

Abstract
A new system for the production of hydrogen, constructed using silica gel as a matrix, Eosin Y as a photosensitizer, and Pt as a cocatalyst, has
been reported. It was found that the rate of photosensitized hydrogen evolution in the presence of silica gel is enhanced about 10-fold relative to
the homogeneous phase, i.e. in the absence of silica gel. The pH value of the solution and the concentration of Eosin Y have remarkable effects on
the rate of hydrogen evolution. The optimal pH and concentration of Eosin Y are 7 and 3.60 × 10−4 mol dm−3 (E/S = 1/3) to 7.24 × 10−4 mol dm−3
(E/S = 1/1), respectively. Triethanolamine (TEOA) as an electron donor, the rate of hydrogen evolution and the apparent quantum efficiency in the
silica gel system under visible-light irradiation (λ ≥ 420 nm) can reach about 43 ␮mol h−1 and 10.4%, respectively. In addition, the roles of silica
gel, Pt and TEOA, respectively; and the probable mechanism of photosensitized hydrogen evolution have been discussed.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Photosensitized; Silica gel; Eosin Y; Hydrogen evolution; Visible-light irradiation

1. Introduction photocatalysts (e.g. CdS) are liable to lose their activities after
long-term irradiation. From a practical point of view, the devel-
From the viewpoint of the solar energy conversion, photo- opment of an active and stable catalyst driven by visible-light
catalytic production of hydrogen by splitting water has been for the photodecomposition of water into hydrogen is urgently
considered a promising technology since photochemical hydro- required. Therefore, many attempts, such as doping, sensitiza-
gen evolution under UV light irradiation was found in the early tion, etc. have been made to extend the optical absorption edge
1970s [1]. Many semiconductors, such as TiO2 [2], SrTiO3 [3], or/and to improve the stability. In 1991, Grätzel et al. proved
CdS [4] and so on, have been investigated for photocatalytic spectra sensitization, as a strategy for effective visible-light har-
splitting water into hydrogen. In recent researches, some solid vest, to be feasible [8]. They improved the photon-to-electric
solution catalysts have also been reported to be active photo- current conversion efficiency up to 7.1% using a ruthenium
catalysts for H2 O decomposition [5–7]. Although remarkable complex-sensitized porous TiO2 film with an extremely high
improvements have been made in photocatalytic hydrogen pro- surface area. It is generally accepted that the success of the dye-
duction in the past decades, there are still some urgent problems sensitized solar cells (DSC) mainly depends on the fact that a
to be resolved at the present time. For example, many stable larger number of sensitizers can be adsorbed [8–10]. Experi-
semiconductors, such as TiO2 , Ta2 O5 , SrTiO3 , etc. are active mentally, it is also proved that porous films are beneficial to
only in the ultraviolet region that only accounts for less than the transfer of the interfacial charge, and further promote the
5% of the solar spectrum. In contrast, some visible-light-driven efficiency of the utilization of charge [11].
Indeed, the spectral sensitization of wide band semicon-
ductors in the solar energy conversion systems involving the
∗ Corresponding author. Tel.: +86 931 4968178; fax: +86 931 4968178. photolysis of water to produce hydrogen has been studied
E-mail address: [email protected] (G. Lu). actively. For example, Abe et al. used dye-sensitized Pt/TiO2 as

0378-7753/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jpowsour.2006.12.082
 X. Zhang et al. / Journal of Power Sources 166 (2007) 74–79 75

a photocatalyst for hydrogen evolution from a water–acetonitrile alytic experiment, 60 mg the composite of Eosin Y and silica gel
mixed solution [12]. Although the dye-sensitized solar cell H was suspended in 60 ml aqueous TEOA (15%, w/w) solution
(DSC) is a good example of spectral sensitization of wide band containing 2.8 ml 7.67 × 10−7 mol dm−3 H2 PtCl6 unless other-
semiconductors, the idea developed from DSC works less effi- wise stated. Prior to irradiation, the suspension of the catalyst in
ciently in the exploitation of photocatalysts used for hydrogen the cell was dispersed for 1 min in an ultrasonic bath, and then
evolution. For instance, the photoenergy conversion efficiency Ar gas was bubbled through the reaction mixtures for 40 min to
and the stability of photocatalysts cannot be satisfied. remove oxygen.
It has been reported that the separation of products formed in To investigate the effect of pH value on the rate of hydro-
photoinduced electron-transfer processes is essential [13]. So, gen evolution, the pH values of the solution determined on a
for the efficient solar energy conversion and storage, several Markson model 6200 pH meter were adjusted by the addition of
other approaches, such as micelle [14,15], liposomes [16,17], hydrochloric acid or sodium hydroxide as required.
microemulsion [18,19], and polyelectrolytes [20,21] in addi- The photocatalytic activity was determined by measuring the
tion to semiconductors, have been adopted to assist the charge amount of hydrogen evolved using a gas chromatograph (TCD,
separation. Because silica gel has a very high and negative sur- molecular sieve 13X column, Ar as gas carrier). The apparent
face charge density that can promote charge separation, Willner quantum efficiency (ΦH2 ) is defined as follows:
et al. used silica gel as a means to control the photosensitized
(mole of hydrogen evolved)
electron-transfer reaction [22]. In addition, silica gel has many ΦH2 = 2 × (1)
other merits, such as high specific surface area and high trans- (mole of incident photon)
parency of visible-light. To the best of our knowledge, there is no In measuring the apparent quantum efficiency, the average
report on photosensitized hydrogen production in organic dye photon flux of the incident light, which is 230 ␮mol (pho-
and silica gel systems at present. ton) m−2 s−1 , was determined with a Ray virtual radiation
In the current study, we chose silica gel as a matrix to adsorb actinometer (FU 100, Silicon ray detector, light spectrum:
dye molecules and to promote the separation of products pro- 400–700 nm, sensitivity: 10–50 ␮V ␮mol−1 m−2 s−1 ), and then
duced in photosensitized electron-transfer reactions, Eosin Y the apparent quantum efficiency was calculated according to Eq.
as a photosensitizer and Pt as a cocatalyst. In the presence of (1).
triethanolamine (TEOA) as an electron donor, the hydrogen UV–vis diffuse reflectance spectra (UV–vis DRS) of the
evolution activity of the system under visible-light irradiation samples were obtained using a U-3010 UV–vis spectrome-
(λ ≥ 420 nm) has been studied. The effects of pH value and ter and were converted from reflectance to absorbance by the
the Eosin Y concentration on the photocatalytic activity for Kubelka–Munk method. UV–vis absorbance spectra of the sam-
hydrogen evolution have been investigated. In addition, the ples were recorded on a HP8453 spectrophotometer. The BET
roles of silica gel, Pt and TEOA, respectively; and the prob- surface area and pore size distributions were obtained by mea-
able mechanism for photosensitized hydrogen evolution have suring N2 adsorption isotherms at 76.2 K using an ASAP 2010V
been discussed. surface analyzer, with a pretreatment temperature of 473 K.

2. Experimental 3. Results and discussion

Commercially available Eosin Y (2 ,4 ,5 ,7 -tetrabromo- 3.1. Characterization of catalyst
fluorescein, disodium salt) and silica gel H (for thin-layer
chromatography) were used without further purification. Other The specific surface area of silica gel H was found to be
chemicals used in our experiments were of analytic reagent. ∼362 m2 g−1 , and the average pore diameter was 9.9 nm using
Loading of the dye sensitizer onto silica gel H was performed the BET method.
by an impregnation method with water as the solvent, that is, It is generally accepted that xanthene dyes exhibit substan-
Eosin Y and silica gel H were simply mixed and stirred for 16 h tial aggregation effects at high concentrations [24,25]. Eosin
in order that Eosin Y could be adsorbed onto silica gel H, and Y, one of xanthene dyes, tends to form dimers or larger aggre-
then dried at 333 K overnight. The weight ratio of Eosin Y and gates in concentrated solution. The absorption spectrum of Eosin
silica gel H (hereafter denoted as E/S) in the photocatalysts by Y dimers displays a doublet with maximums at 485 nm and
an impregnation method is 1/2 unless otherwise stated. In order 540 nm, corresponding to the H-type dimer and J-type dimer,
to enhance the photocatalytic activity for hydrogen evolution, Pt respectively [25]. Fig. 1 shows the UV-vis absorption spectrum
particles were loaded in situ by a photochemical method, which of the 6.00 × 10−5 mol dm−3 Eosin Y in aqueous silica gel H at
is similar to the method described in the reference [23], with an pH 7. It can be seen that the spectrum shows a peak at around
aqueous solution of H2 PtCl6 . 510 nm with a shoulder at ca. 485 nm. These bands are attributed
A 300 W tungsten halogen lamp, equipped with a 420 nm to that of the monomer and the dimer (H-type) of Eosin Y,
cut-off filter (Toshiba, S Y44.2), was used as the light source. respectively.
The photocatalytic reaction was carried out in a Pyrex flask of ca. The UV–vis diffuse reflectance spectra of silica gel H, Eosin
108 ml with a flat window (with an efficient irradiation area of ca. Y and the composite of Eosin Y and silica gel H are shown in
10 cm2 ). The reaction mixtures inside the cell were maintained in Fig. 2. The absorption band edge of the composite of Eosin Y and
suspension by means of a magnetic stirrer. In a typical photocat- silica gel H is apparently red shifted to about 600 nm compared
76 X. Zhang et al. / Journal of Power Sources 166 (2007) 74–79

Fig. 1. UV–vis absorption spectrum of 6.00 × 10−5 mol dm−3 Eosin Y in aque- Fig. 3. Dependence of the average rate of hydrogen evolution upon pH. Reac-
ous silica gel H at pH 7. Inset is partial magnification of the absorption spectrum. tion conditions: 60 mg the composite of Eosin Y and silica gel H (E/S = 1/2),
irradiation time 10 h, Ar-saturated. Inset describes the apparent photon quantum
efficiency as a function of pH.
to that of silica gel H and blue shifted by ca. 50 nm compared
to that of Eosin Y, which implies that it is possible that some
interactions (e.g. hydrogen bond) between Eosin Y and silica In particular, when the pH value of the solution was adjusted to
gel H exist. 2, 3 or 4, no hydrogen evolution was observed. The following
are the reasons for rationalizing this phenomenon.
First, the pH value of the solution might have effects on the
3.2. Effect of pH on the rate of hydrogen evolution
form of TEOA in aqueous solution and its adsorption on the sur-
face of silica gel H. On the one hand, in strongly acidic solution,
In general, pH values have notable effects on the photocat-
the protonated TEOA is hard to be adsorbed onto the surface
alytic activity for hydrogen evolution. Fig. 3 shows the effect of
of silica gel H because of electrostatic repulsion force resulting
the pH value of the solution on the average rate of hydrogen evo-
from the protonation of hydroxyl groups on the surface of silica
lution from an aqueous TEOA solution. When pH values vary
gel H. On the other hand, the ability of donating electrons would
from 2 to 13, the maximum average rate of hydrogen evolution
weaken because the electron donor TEOA undergoes total pro-
and apparent quantum efficiency, about 43 ␮mol h−1 and 10.4%,
tonation [26]. As a result, the lifetime of the excited Eosin Y and
respectively, are achieved at pH 7, and either the strongly acidic
regeneration of Eosin Y might be affected, which results in the
or strongly basic solution is detrimental to hydrogen evolution.
low rate of hydrogen evolution.
Second, the pH value of the solution might have an effect
on the interactions between Eosin Y and silica gel. It has been
reported that silica gel particles are negatively charged at pH ≥6
[22]. In strongly basic solution, Eosin Y exists in the bivalent
anionic form. As a result, dye species are difficult to interact
with the surface of silica gel because of electrostatic repulsion
force.
Third, the pH value of the solution could affect the reactions
of hydrogen evolution and TEOA oxidation. Since the reaction
of hydrogen evolution involves the reduction of H+ , the rate
of hydrogen evolution should depend on the concentration of
H+ . The higher the concentration of H+ , the faster the reduction
of H+ would proceed. However, Kalyanasundaram et al. have
reported that TEOA is oxidized by means of losing one of the
unpair electron of the N atom [27], so the protonated forms of
TEOA are difficult to oxidize. As a result, the photosensitized
hydrogen evolution process should occur at an optimized pH.
In addition, it has been reported that dispersive force,
Fig. 2. UV–vis diffuse reflectance spectra of silica gel H, Eosin Y and the hydrophobic force as well as electrostatic force provide a major
composite of Eosin Y and silica gel H. (a) Silica gel H, (b) Eosin Y, and (c) the contribution to the aggregation of Eosin Y [25]. When the sys-
composite of Eosin Y and silica gel H. tem is in strongly basic solution, Eosin Y is difficult to aggregate
 X. Zhang et al. / Journal of Power Sources 166 (2007) 74–79 77

to form dimers when electrostatic repulsion force between biva-

lent anionic forms of the monomer Eosin Y is stronger than
dispersive force and hydrophobic force. However, the dimers
could play an extraordinary role in the photosensitized electron-
transfer process, which will be discussed below. Consequently,
in strongly basic solution, the rate of hydrogen evolution is very
low.

3.3. Effect of concentration of Eosin Y on the rate of

hydrogen evolution

Fig. 4 shows the effect of the Eosin Y concentration,

0–9.60 × 10−4 mol dm−3 (E/S = 2/1), on the average rate of
hydrogen evolution from an aqueous TEOA solution at pH 7. As
shown in Fig. 4, when the concentration of Eosin Y is in the range
of 3.60 × 10−4 mol dm −3 (E/S = 1/3) to 7.24 × 10−4 mol dm−3
(E/S = 1/1), the rate of hydrogen evolution is relatively high, Fig. 5. Dependence of the ratio of peak intensity I1 /I2 upon the concentration
about 43 ␮mol h−1 , when the apparent quantum efficiency is of Eosin Y in TEOA aqueous solution at pH 7.
ca. 10%. If no Eosin Y is added, then no hydrogen evolu-
tion is observed. When the concentration of Eosin Y is lower
intersystem crossing as well as radiative and nonradiative tran-
than 3.60 × 10−4 mol dm−3 (E/S = 1/3), the rate of hydrogen
sition [28]. The higher the concentration of Eosin Y, the closer
evolution increases with increasing the concentration. On the
the distance between adjacent dye species on the silica gel sur-
contrary, when the concentration of Eosin Y is higher than
face, the more efficient the concentration quenching, and the
7.24 × 10−4 mol dm−3 (E/S = 1/1), the rate of hydrogen evolu-
less efficiency utilized by the excited dye species. On the other
tion decreases with increasing the concentration. The following
hand, it may result from the decrease in the number of the pho-
are the reasons for explaining these behaviors.
ton absorbed by Eosin located on the surface of silica gel. When
The first, as shown in Fig. 2, silica gel H dose not absorb the
the concentration of Eosin Y is relatively higher, the number
visible light (λ ≥ 420 nm), so no hydrogen evolution is observed
of Eosin Y adsorbed increases hardly with increasing the con-
in the absence of Eosin Y.
centration of Eosin Y. As a result, the absorbance of Eosin Y
The second, in order to rationalize the phenomenon that
free in solution increases. Consequently, the number of the pho-
the rate of hydrogen evolution decreases with increasing
ton absorbed by Eosin Y adsorbed on the surface of silica gel
the concentration at a higher Eosin Y concentration (e.g.
decreases. However, as it will be discussed below, the interac-
≥7.24 × 10−4 mol dm−3 , E/S = 1/1), we consider first concen-
tions between silica gel and Eosin Y have remarkable effects on
tration quenching. When the concentration of Eosin is relatively
the rate of hydrogen evolution.
high, the deactivation of excited dye species could be easier via
The third, it could be caused by the increase in the Eosin
Y dimers that the rate of hydrogen evolution increases with
increasing the Eosin Y concentration (≤3.60 × 10−4 mol dm−3 ,
E/S = 1/3). The intensities of peaks at 510 nm and 485 nm are
denoted as I1 and I2 , respectively. The ratio of I1 /I2 represented
the ratio of the concentration of monomer and dimer in the solu-
tion. Fig. 5 describes the effect of the concentration on the ratio
of I1 /I2 . It can be seen that the I1 /I2 ratio drops with increasing
the concentration of Eosin Y, that is, the concentration of the
dimer increases when the concentration of Eosin Y is increased.
The result is in accordance with what De et al. reported before
[25]. The photosensitized electron transfer could be carried out
via the dimers, so the rate of hydrogen evolution increases when
the concentration of Eosin Y is increased.

4. Mechanism

4.1. Role of silica gel H

Fig. 4. Dependence of the average rate of hydrogen evolution upon E/S. Reaction
Fig. 6 compares the rate of hydrogen evolution in the pres-
conditions: 60 mg the composites of Eosin Y and silica gel H, pH 7, irradiation
time 10 h, Ar-saturated. Inset describes the apparent photon quantum efficiency ence and absence of silica gel H (40 mg) from an aqueous
as a function of E/S. TEOA solution at pH 7 when the concentration of Eosin Y is
78 X. Zhang et al. / Journal of Power Sources 166 (2007) 74–79

It is noteworthy that EO (referred here and hereafter) repre-

sents Eosin Y species.

4.2. Role of Pt

Whether in the presence or absence of silica gel in the sys-

tem, Pt has a remarkable effect on the rate of photosensitized
hydrogen evolution. When 60 mg the composite of Eosin Y
and silica gel H was suspended in 60 ml aqueous TEOA solu-
tion at pH 7, the average rate of hydrogen evolution was only
3.5 × 10−2 ␮mol h−1 under visible-light irradiation. However,
when Pt particles were loaded, the rate of hydrogen evolution
was enhanced remarkably and about 43 ␮mol h−1 . Similarly, the
rate of hydrogen evolution in the absence of silica gel was only
2.3 × 10−2 ␮mol h−1 without Pt particles loaded, while the rate
was about 4 ␮mol h−1 in the presence of Pt particles. The rea-
sons that the rate of hydrogen evolution is enhanced significantly
Fig. 6. Time courses of hydrogen evolution from an aqueous TEOA solution. in the presence of Pt particles are as follows.
Reaction conditions: 20 mg Eosin Y, pH 7, Ar-saturated. (a) In the presence of On the one hand, since the overpotential of hydrogen on
silica gel H (40 mg); (b) in the absence of silica gel H. Pt is rather low, hydrogen evolution is easier in the presence
of Pt particles. On the other hand, it has been reported that
3.60 × 10−4 mol dm−3 . It can be seen that the rate of hydrogen metal nanoparticles (e.g. Au and Ag) can accept electrons from
evolution in the absence of silica gel H is about 4 ␮mol h−1 . sensitizers in metal particle-sensitizer nanoassemblies under
In addition, the rate of hydrogen evolution in the presence of photoexcitation [30,31]. Based on the fact, we inferred that Pt
silica gel H is enhanced about 10-fold relative to the homoge- particles could play a similar role. Consequently, the rate of the
neous phase, i.e. in the absence of silica gel H. On the basis regeneration of dye species would be enhanced, the back reac-
of the results above, we conclude that silica gel H can accel- tion of EO•+ and EO•− would be retarded and the efficiency of
erate the rate of hydrogen evolution, but it is not essential the utilization of excited dye species would be improved. Finally,
for the photosensitized hydrogen evolution process. We think the rate of hydrogen evolution is enhanced remarkably.
that the enhanced rate of hydrogen evolution in the presence
of silica gel H particles can be partly ascribed to the con- 4.3. Role of TEOA
trol of the electron-transfer reaction by means of electrostatic
interaction. The idea is developed from the following consider- TEOA could play a key role in the photosensitized hydro-
ations. gen evolution process. The reason is that no hydrogen evolution
On the one hand, it has been reported that silanol groups on was observed under visible-light irradiation for 40 h when 60 mg
the particle surface are ionized at pH ≥6. Consequently, in neu- the composite of Eosin Y and silica gel H was suspended in
tral or basic solution, the surface of the particle is negatively 60 ml aqueous solution containing a certain amount of H2 PtCl6
charged and a diffuse electrical double layer is produced in the at pH 7. The functions of TEOA in the photosensitized hydrogen
vicinity of the solid interface. The particles could be used to evolution process could be demonstrated in the following two
exert electrostatic repulsive and attractive interactions with the aspects:
components involved in photosensitized reactions [22]. On the On the one hand, TEOA, as an electron donor, could quench
other hand, it has been proposed by Pelet et al. that EO•+ and the excited dye species to the ground state by means of reacting
EO•− could be produced via intermolecular electron transfer with the oxidized dye species, i.e. EO•+ . On the other hand, it
within Eosin Y dimer yielding (EO•+ EO•− ) radical pairs on the could enhance the stability of (EO•+ EO•− ) radical pairs through
surface of the nonreactive oxide (e.g. Al2 O3 and ZrO2 ) [29]. The the Van der Waals interaction with these species. As a result, the
charged interface provided by silica gel interacts with EO•+ and production of (EO•+ EO•− ) radical pairs would be easier and the
EO•− produced. The positively charged dye species, i.e. EO•+ , lifetime of (EO•+ EO•− ) radical pairs would be prolonged.
are adsorbed on the interface by means of electrostatic attrac-
tive interactions, while the negatively charged dye species, i.e. 4.4. Inference of photosensitized hydrogen evolution
EO•− , are repelled by means of electrostatic repulsive interac- mechanism
tions. Consequently, the separation of EO•+ and EO•− would
be promoted. By comparing the potential of the conduction band of SiO2
In addition, silica gel can supply enough large interfaces (∼−4.2 V (vs. NHE)) [32] and the EO* (S1)/EO•+ couple
because of its high specific surface area, so that Pt particles (E◦ = −1.2 V (vs. NHE)) [28], the probability of electron injec-
as the active centers for hydrogen evolution can be highly dis- tion from the excited dye species to the conduction band of
persed. As a result, the rate of hydrogen evolution is enhanced SiO2 is ruled out. In the case of the reaction system in this study,
remarkably. the electron transfer could be carried out via (EO•+ EO•− ) rad-
 X. Zhang et al. / Journal of Power Sources 166 (2007) 74–79 79

only regenerate the dye species, but also enhance the stability of
(EO•+ EO•− ) radical pairs through the Van der Waals interac-
tion with these species and further enhance the rate of hydrogen
evolution.

Acknowledgements
Scheme 1. Probable mechanism of photosensitized hydrogen evolution (note
that EO, D and Dox represent the sensitizer, the electron donor, and the oxidized The financial supports from the National Natural Science
product of electron donor, respectively). Foundation of China (No. 90210027) and the National Basic
Research Program of China (No. 2003CB214500) are gratefully
ical pairs produced through the intermolecular electron transfer acknowledged.
within Eosin Y dimers. Based on the discussion above, a fea-
sible mechanism for the photosensitized hydrogen evolution is References
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