Microporous and Mesoporous Materials 87 (2005) 1–9

www.elsevier.com/locate/micromeso

Nanosize and bimodal porous polyoxotungstate–anatase

TiO2 composites: Preparation and photocatalytic degradation
of organophosphorus pesticide using visible-light excitation
a,b c,* a,* d
Li Li , Qing-yin Wu , Yi-hang Guo , Chang-wen Hu
a
Faculty of Chemistry, Northeast Normal University, Changchun 130024, PR China
b
Faculty of Chemistry and Chemical Engineering, Qiqihar University, Qiqihar 161006, PR China
c
Department of Chemistry, Zhejiang University, Hangzhou 310027, PR China
d
Department of Chemistry, Beijing Institute of Technology, Beijing 100081, PR China

Received 4 December 2004; received in revised form 3 March 2005; accepted 25 July 2005
Available online 16 September 2005

Abstract

New and efficient heterogeneous photocatalytic materials, H3PW12O40/TiO2 and H6P2W18O62/TiO2, with anatase crystalline
phase, dual-pore structures (micro- and meso-porosity), and nanometer sizes (average particle size of 6 nm) were prepared by com-
bination of the methods of sol–gel and hydrothermal treatment at a lower temperature (200 °C, 2 °C/min). Compositions, struc-
tures, physicochemical properties, and surface morphology of the composites were characterized by inductively coupled plasma
atomic emission spectrum (ICP-AES), X-ray diffraction (XRD) patterns, UV diffuse reflectance spectroscopy (UV/DRS), 31P
magic-angle spinning (MAS) NMR, Raman scattering spectra, nitrogen adsorption/desorption determination, and transmission
electron microscopy (TEM), respectively. It indicated that the primary Keggin or Dawson structure remained intact after immobi-
lization of the unit into TiO2 network, and hydrogen bonding and chemical interactions between the unit and the anatase network
existed in the composites. Both of the composites exhibited visible-light photocatalytic activity to degradation of an aqueous orga-
nophosphorus pesticide, parathion-methyl, and the deactivation of the catalysts was hardly observed after five times catalytic
cycling.
Ó 2005 Elsevier Inc. All rights reserved.

Keywords: Hydrothermal treatment; Porous materials; Polyoxometalate; Sol–gel; Visible-light photocatalysis

1. Introduction vides some opportunities for them. Anatase TiO2 is the

Heterogeneous photocatalytic destruction of organic
pollutants in wastewater by using solar light (or light
from the visible region of the spectrum) as the excitation
energy is an appealing field [1–5]. To meet the need of
this, it is important to design and prepare efficient
photocatalytic materials, which may then appear to be
a challenge to the chemists, at the same time, it also pro-
*
Corresponding authors. Tel.: +86 431 5099371; fax: +86 431
5692259.
E-mail address: guoyh@nenu.edu.cn (Y.-h. Guo).
most widely investigated heterogeneous semiconductor
photocatalyst [6–8], while polyoxometalates (POMs)
have been studied as a homogeneous photocatalyst
[9–13]. Both of TiO2 and POMs share the very similar
photocatalytic processes owing to their similar elec-
tronic attribute. However, they must be activated in
the near-UV area due to their wide band gap. In addi-
tion, for the purpose of practical application of this
technique, immobilization of soluble POM into some
matrixes to prepare solid or supported POM photocata-
lysts is essential. Our previous work have prepared sev-
eral water-insoluble POMs by immobilizing them into

1387-1811/$ - see front matter Ó 2005 Elsevier Inc. All rights reserved.
doi:10.1016/j.micromeso.2005.07.035
2 L. Li et al. / Microporous and Mesoporous Materials 87 (2005) 1–9
silica matrix via soft chemical preparation techniques
including sol–gel, templating, intercalating, and hydro-
thermal treatment [14–18]. These insoluble POM/SiO2
composites had different pore sizes (i.e., micro-, meso-
and macro-pores), and they exhibited much higher
UV-photocatalytic activity than that of the correspond-
ing pure or homogeneous POMs. Moreover, it is easy to
separate and recover them for recycling purpose. But the
main disadvantage of these POM/SiO2 composites is
that they show little activity under visible-light irradia-
tion. In order to improve the photoefficiency of either
POM or TiO2, and immobilization of soluble POM,
we here prepared two POM-containing anatase TiO2
composites (H3PW12O40/TiO2 and H6PW18O62/TiO2)
via combining the methods of sol–gel and hydrothermal
treatment with a constant heating rate (2 °C/min to
200 °C). The motivation for this design is based on the
structural characteristics of either TiO2 or POM. That
is, POM has empty d orbits and can be used as good
electron acceptors. After the addition of POM into
TiO2 photocatalytic systems, the fast charge-pair (h+–
e
) recombination on TiO2 can be retarded effectively.
That is, POM has the ability to enhance the rate of con-
duction band (CB) electron transfer by accepting e

(photogenerated electrons) to its empty d orbits. Several
research groups have studied this synergistic effect ex-
isted between TiO2 and POM. For example, Ferry
reported that significant rate enhancement for 1,2-
dichlorobenzene photooxidation was obtained after
addition of aqueous photoactive POM anions including
PW12 O3
4
4

40 , SiW12 O40 , or W10 O32 into TiO2 suspensions
[19]. Choi reported that the addition of homogenous
SiW12 O4
40 into the naked TiO2 suspension greatly in-
creased the photocatalytic oxidation rate of As(III) to
As(V), which is less toxic and less mobile in the aquatic
environment [20]. And they pointed out that the pres-
ence of POMs enhances the generation of superoxides,
which are the main oxidant of As(III). Choi further
proved this synergistic effect occurred between POM
and TiO2 through photoelectrochemical investigation
[21]. They concluded that POMs successfully transfer
CB electrons on TiO2 particles to an inert collector elec-
trode with generating photocurrents under UV illumina-
tion. The magnitude of photocurrent is directly
proportional to the reduced POM concentration and
markedly decreases in the presence of dissolved O2 due
to the rapid reoxidation of the reduced POM by O2.
However, in the above TiO2–POM systems, POMs were
in the homogeneous phases, they dissolved in the reac-
tion systems, thus separating them for recycling applica-
tions is very difficult. Here, as-prepared POM/TiO2
composites are insoluble and they have the characteris-
tics such as narrow band gap, dual-pore structures
(micro- and meso-porosity), nanometer size (<10 nm),
and much larger BET surface area (BET surface area
for anatase TiO2 is 53.2 m2/g [21], and for POM is lower
than 10 m2/g, [23]). More importantly, the interactions
between the Keggin (or Wells–Dawson) unit and TiO2
support is chemical rather than physical, which ensure
little leakage of them from TiO2 matrix during the pro-
cess of catalysis, therefore, the composites can be reused
more than five times without finding obvious decreases
of their photocatalytic activity. The above described cat-
alytic result was obtained via the test of visible-light
photocatalytic degradation of an aqueous parathion-
methyl, a kind of stable organophosphorus pesticide.
Parathion-methyl had only absorption at 280 nm, and
it did not suffer any degradation with 4 h direct photol-
ysis under visible-light irradiation. However, its signifi-
cant degradation was obtained under visible-light
irradiation, the suspension of an aqueous parathion-
methyl and the POM/TiO2, whereas, the starting
H3PW12O40 or H6P2W18O62, and commercial available
Degussa P 25 exhibited little visible-light photocatalytic
activity to degradation of it. As for the nanosize anatase
TiO2 (average size lower than 10 nm) prepared in the
present work, only substrate adsorption rather than deg-
radation was observed during the process of visible-light
irradiation of it.
2. Experimental
2.1. Photocatalyst preparation and characterization
A typical method of preparation of H3PW12O40/TiO2
or H6P2W18O62/TiO2 composites is described below.
Titanium tetraisopropoxide (TTIP, 98%, 20 mmol) was
dissolved with iso-propyl alcohol (392 mmol) while stir-
ring was used. In another container, H3PW12O40 or
H6P2W18O62 (0.13 mmol) was dissolved with water
(44 mmol), and then added into the TTIP solution drop
by drop. The resulting mixture was adjusted to pH 1–2
by addition of 8 mol/l HCl, and it was stirred at room
temperature for 1 h, and then heated to 45 °C until
homogeneous H3PW12O40/TiO2 or H6P2W18O62/TiO2
hydrogel was formed. This hydrogel was transferred
into an autoclave, and then heated to 200 °C with a rate
of 2 °C/min. Finally, the temperature was kept at 200 °C
for 1 h. This hydrogel was cooled to room temperature
and dehydrated slowly at 50 °C in a vacuum for 24 h.
The dried gel was washed with hot water and dried at
room temperature.
Elemental analysis for H3PW12O40/TiO2: P, 0.21%;
W, 14.4%; H3PW12O40, 19.61%. Elemental analysis for
H6P2W18O62/TiO2: P, 0.31%; W, 16.28%; H6P2W18O62,
21.52%. The above data were determined with a Leeman
Plasma Spec (I) ICP-AES.
XRD patterns were obtained with a Rigaku D/max
2000 X-ray diffractometer with Cu-Ka radiation. UV/
DRS were recorded on a Cary 500 UV–VIS–NIR spec-
trophotometer. 31P MAS NMR spectra were obtained
 L. Li et al. / Microporous and Mesoporous Materials 87 (2005) 1–9
on a Varian Unity-400 NMR spectrometer. Raman
spectra were recorded on a Jobin-Yvon HR 800 instru-
ment with an Ar+ laser source of 488 nm wavelength in
a macroscopic configuration. TEM micrographs were
obtained on a JEOL JEM-2010 transmission electron
microscope at an accelerating voltage of 200 kV. BET
specific surface areas, pore sizes and pore volumes were
calculated from nitrogen adsorption/desorption iso-
therm determined at
196 °C using an ASAP 2010 M
surface analyzer (the samples were outgassed under vac-
uum at 200 °C).
2.2. Photocatalytic degradation of an aqueous
parathion-methyl using visible-light excitation
The photoreactor was designed with a cylindrical
glass cell configuration and an internal visible-light
source (400 W Xe lamp) surrounded by an optical glass
jacket (UV spectrum of Xe lamp was cut out through
this optical glass jacket, which has complete absorption
in the range of 190–330 nm), where the suspension of the
solid catalyst (H3PW12O40/TiO2 or H6P2W18O62/TiO2,
0.2 g) and aqueous parathion-methyl (150 ml, 50 mg l
1)
totally surrounded the light source. The acidity of the
suspension was neutral. The temperature of the suspen-
sion was maintained at 35 ± 2 °C by circulating water
through an external cooling coil, and the system was
open to air. During the process of the photocatalytic
tests, parathion-methyl was monitored by a Shimadzu
LC-8A high pressure liquid chromatography (HPLC)
equipped with a C18 column and a UV detector
(k = 280 nm). Before HPLC determination, the with-
drawn suspensions were centrifuged and filtered with
the membrane. The intermediates and final products
yielded during the course of photodegradation of the
parathion-methyl were identified by a DX-300 ion chro-
matograph (IC) equipped with a conductivity detector
and AS4A or ICE-ASI column.
3. Results and discussion
3.1. Preparation and characterization of H3PW12O40/
TiO2 and H6P2W18O62/TiO2 composites
Preparation of the H3PW12O40/TiO2 or H6P2W18O62/
TiO2 composite included two steps. At first, H3PW12-
O40/TiO2 or H6P2W18O62/TiO2 sol was obtained via
Table 1
Characteristic diffraction peaks of 2h values (20–80 °C) for TiO2, H3PW12O40/TiO2, and H6P2W18O62/TiO2
Sample 101 103
TiO2 25.21 37.90
H3PW12O40/TiO2 25.29 37.94
H6P2W18O62/TiO2 25.29 36.07
3
hydrolysis of titanium TTIP in the presence of acidic
inorganic precursor such as H3PW12O40 or H6P2W18-
O62. In this step, polycondensation reaction occurred
simultaneously, which induced polymerization forming
higher molecular weight products, i.e., H3PW12O40/
Ti(OTi)x(OH)4
x or H6P2W18O62/Ti(OTi)x(OH)4
x.
Second, H3PW12O40/Ti(OTi)x(OH)4
x or H6P2W18O62/
Ti(OTi)x(OH)4
x sol was hydrothermally treated at
200 °C with a rate of 2 °C/min and kept at this temper-
ature for 1 h, then the products were dehydrated and
calcined in vacuum, resulting in the final products,
H3PW12O40/TiO2 or H6P2W18O62/TiO2. During this
process, TiO2 amorphous-anatase phase transition
occurred, which is supported by XRD measurement
(Fig. 1). It showed both H3PW12O40/TiO2 and H6P2-
W18O62/TiO2 composites prepared by sol–gel method
following hydrothermal treatment with a constant heat-
ing rate had a uniform anatase phase (JCPDS File No.
21-1272), and the corresponding characteristic diffrac-
tion peaks of 2h values are summarized in Table 1. Com-
pared with the pure TiO2 prepared here, changes in the
peak positions and widths happened somewhat after
formation of the composites. As for the composites pre-
pared by sol–gel method following hydrothermal treat-
ment at 200 °C without controlling the heating rate
were amorphous (Fig. 1D), suggesting that the key step
to obtain polyoxotungstate–TiO2 composites with ana-
tase structure at a lower temperature (200 °C) is to
maintain a constant heating rate during the process of
hydrothermal treatment the products. On the other
(101)
(211)
(004) (200) (105)
(204) (116) (215) A
Intensity (a.u.)
B
C
D
0 20 40 60 80
2 Theta /degree
Fig. 1. XRD patterns for (A) H6P2W18O62/TiO2, (B) anatase TiO2, (C)
H3PW12O40/TiO2, and (D) amorphous H6P2W18O62/TiO2.
200 105 204 116
47.96 54.32 63.10 75.38
48.00 54.46 62.90 75.23
46.80 54.46 62.58 74.90
4 L. Li et al. / Microporous and Mesoporous Materials 87 (2005) 1–9

31
Fig. 2. P MAS NMR for (A) H3PW12O40/TiO2, and (B) H6P2W18O62/TiO2.

hand, at this relatively lower temperature, thermal

decomposition of polyoxotungstates was avoided totally
(polyoxotungstates begin to decompose at approxi-
mately 350 °C [24]). Except the characteristic diffraction
peaks corresponding to the anatase-type structure, the
peaks with poor crystallinity and 2h values at 6.23 Anatase TiO2
(1 0 0), and 7.05 (1 0 1), respectively, in Fig. 1A were orig-
inated from the starting H6P2W18O62 unit (JCPDS File H6P2W18O62/TiO2
No. 72-2414). Similarly, the peak of 2h value at 6.60
(1 1 1) in Fig. 1C was originated from the starting H6P2W18O62
H3PW12O40 unit (JCPDS File No. 76-1815). These are
the strongest diffraction peaks of pure H6P2W18O62 or
H3PW12O40 unit. 200 400 600 800 1000 1200
The structures of polyoxotungstates in the as-pre- A Raman shift (cm-1)
pared POM/TiO2 composites were further studied by
31
P magic-angle spinning (MAS) NMR (Fig. 2), Raman
scattering spectroscopy (Fig. 3) and UV/DRS (Fig. 4).
Unfortunately, we failed to characterize the structures
of the composites with IR spectroscopy. The reason is
that the intense and broad vibration peaks originated
from Ti–O–Ti bonds in TiO2 framework severely Anatase TiO2
covered the bands corresponding to P–O, W@O, or
W–O–W bond vibrations from polyoxotungstates at H3PW12O40/TiO2
the mid-IR region. The determined chemical shift for
H3PW12O40/TiO2 and H6P2W18O62/TiO2 was
14.0
and
12.9 ppm, respectively, approximately consistent H3PW12O40
with the values originated from the starting Keggin or
Wells–Dawson unit [24]. Some changes of the 31P chem- 0 200 400 600 800 1100 1200
ical shifts suggested that interactions between the poly- Raman shift (cm-1)
B
oxotungstate and the anatase TiO2 exist in the
composites, resulting in the changes of chemical envi- Fig. 3. Raman scattering spectra of (A) H6P2W18O62, TiO2,
ronments of P atoms. Raman scattering studies further H6P2W18O62/TiO2, and (B) H3PW12O40, TiO2, H3PW12O40/TiO2.
confirmed the anatase structure of as-prepared pure
TiO2 and POM/TiO2 in the composites. That is, in the From Raman spectra, we also find the Keggin or
case of pure TiO2, characteristic peaks at 154.4 (Eg), Wells–Dawson unit-relating peaks. That is, the starting
403.2 (B1g), 523.4 (B1g), and 645.7 cm
1 (Eg) originated H3PW12O40-relating Raman peaks were assigned as
from anatase TiO2 [25]. As for the H3PW12O40/TiO2 or follows: i.e., 1001.6 cm
1 (strong), corresponding to
H6P2W18O62/TiO2, we also observed the above four symmetric P–O bond stretching vibrations of the PO4
peaks corresponding to the anatase TiO2. However, sites [26]; 977 cm
1(weak), corresponding to W@O bond
the Eg Raman mode at 154.4 cm
1 shifted to higher stretching vibrations; and 926 cm
1 (weak), correspond-
wave numbers, i.e., 156.4 cm
1 for H6P2W18O62/TiO2 ing to W–O–W bond stretching vibrations [4]. After
and 160.1 cm
1 for H3PW12O40/TiO2, respectively. impregnation of H3PW12O40 into anatase TiO2 crystal
 L. Li et al. / Microporous and Mesoporous Materials 87 (2005) 1–9
0.5
TiO2
0.4
H3PW12O40/TiO2
H6P2W18O62/TiO2
H3PW12O40
0.3
H6P2W18O62
Absorbance
0.2
0.1
0.0
200 250 300 350 400 450 500
Wavelength/nm
Fig. 4. UV/DRS of the anatase TiO2, the starting H3PW12O40 and
H6P2W18O6 2, and the corresponding composites.
lattice, the peaks corresponding to W@O and P–O
bonds vibrations were broadened, therefore, we only ob-
served one wide peak in the range of 935.6–1088.2 cm
1.
At the same time, the peak intensity corresponding to
W–O–W bond vibration became much weaker. Similar
results were found in H6P2W18O62 and H6P2W18O62/
TiO2. That is, the peaks at 1022, 990, and 910 cm
1 were
originated from P–O, W@O, and W–O–W bond vibra-
tions, respectively, in pure H6P2W18O62. After forma-
tion of H6P2W18O62/TiO2 composite, the peaks
corresponding to W@O and P–O bond vibrations were
broadened and appeared at 1012.7 cm
1, and the peak
intensity corresponding to W–O–W bond vibration be-
came very weak. The above changes of Raman shifts
and the decreases of the peak intensities are due to strong
interactions between the Keggin or Wells–Dawson unit
and the anatase TiO2 network, which resulted in the de-
crease of the symmetry of either TiO2 or POM molecules.
Both Keggin and Wells–Dawson unit exhibited a strong
UV absorption at approximately 190 nm, corresponding
to the charge transfer (CT) from O 2p to W 5d occurred
at W@O bonds. As for W–O–W bonds of the units, their
CT band was weaker and appeared at approximately
260 nm for Keggin unit and approximately 302 nm for
Dawson unit, respectively [27]. Anatase TiO2 prepared
in the present work has a strong absorption in the range
of 200–380 nm, corresponding to CT from O 2p to Ti 3d
(i.e., electron excitation from the valence band to con-
duction bond) [4]. After formation of the POM/TiO2
composites, their CT band shifted to a higher wavelength
compared with the starting POM or TiO2, and an
absorption threshold onset that continuously extended
to the visible region (420 nm), which corresponded to a
relatively narrow band gap. This result suggests that
the presence of Keggin or Dawson unit also has an influ-
ence on the electronic properties of anatase TiO2 in as-
prepared composites. Similar energy of Ti 3d and W 5d
levels would suggest that the POM doping in an anatase
5
only produced moderate widening of electronic band
(similar crystal field splitting for both cations, just
slightly differing in the d orbital average size). Redshift
of OMCT (oxygen to metal charge transfer) band indi-
cates that there is a doping energy level between the con-
duction and valence bands of TiO2, and the electronic
properties of the composites resulted from the following
two transition forms. One is the transition from the va-
lence band to the conduction band (corresponding to
wide band gap), and the other is the transition from
the valence band to the doping energy level (correspond-
ing to narrow band gap).
From the above results of XRD, 31P MAS NMR,
Raman scattering spectroscopy, and UV/DRS, we con-
clude that the primary Keggin or Dawson structure re-
mained intact after formation of the composites. The
changes including chemical shifts in 31P MAS NMR,
Raman shifts and the peak broadening in Raman scat-
tering spectroscopy, and redshift of the OMCT band
indicted that the strong interactions between the
POM anions and TiO2 network existed in the compos-
ites. According to the structural characteristics of H3-
PW12O40 or H6P2W18O62 and TiO2 network, we inferred
these interactions between the two components were
hydrogen bonding and acid basic. At first, hydrogen
bonds were formed in the composites between oxygen
atoms of the Keggin or Dawson anion and the surface
hydroxyl groups (Ti–OH) of the anatase TiO2 network,
which can be expressed in the forms of W@Ot   
HO–Ti, W–Oc    HO–Ti, and W–Oe  HO–Ti, where
Ot and Oc or Oe referred to the terminal oxygen atoms
and the bridge oxygen atoms, respectively, in the POM
units. In addition, chemically active surface Ti–OH
groups were protonated in an acidic medium to form
Ti–OHþ þ
2 groups. Ti–OH2 group should act as a counter
ion for H3PW12O40 or H6P2W18O62 unit and yielded
ðTi–OHþ
þ

2 ÞðH2 PW12 O40 Þ or ðTi–OH2 ÞðH5 P2 W18 O62 Þ by
acid–base reaction. The process is described in Eqs. (1)
and (2). This interaction also was confirmed in the
micro-porous H3PW12O40/SiO2, H4SiW12O40/SiO2, and
Na4W10O32/SiO2 composites [14,17].
Ti–OH þ H3 PW12 O40 ! ðTi–OHþ

2 ÞðH2 PW12 O40 Þ ð1Þ
Ti–OH þ H6 P2 W18 O62 ! ðTi–OHþ

2 ÞðH5 P2 W18 O62 Þ ð2Þ
TEM images (Fig. 5) of the two composites show that
the particles are sphere-like and exhibited uniform size
distribution with an average size of 6 nm, and aggrega-
tion among particles was also observed in these two
images. The rings recorded from the selected area elec-
tron diffraction (SAED) of the sample were indexed to
diffraction from the (1 0 1), (0 0 4), (2 0 0), (1 0 5), (2 0 4),
(1 1 6), and (2 1 5) planes of anatase, consistent with the
above XRD results. Formation of these tiny sizes of
as-prepared composites is closely related to the current
prepared method.
6 L. Li et al. / Microporous and Mesoporous Materials 87 (2005) 1–9
Fig. 5. TEM images of (A) H6P2W18O62/TiO2, and (B) H3PW12O40/TiO2.
Very interestingly, the composites exhibited bimodal
pore systems (micro-mesoporosity) with pore size at
approximately 0.6 and 4.0 nm, respectively, from the
nitrogen adsorption–desorption analysis (Fig. 6). That
is, the curves show two well-defined adsorption steps.
The first, at very low relative pressure (p/p0 < 0.1), the
isotherms exhibit high adsorption, indicating that the
powders contain micro-pores (Type I). In addition,
t-plot (Fig. 6B) obtained from the nitrogen adsorption–
S
visible light
(OH3C)2 P O NO2
H3PW12O40/TiO2 or
H6P2W18O62/TiO2
desorption determination did not cross through zero,
also suggesting some micro-pores existed in the compos-
ite. The second, at an intermediate relative pressure (p/
p0 = 0.4–0.8), the curves exhibit a hysteresis loop, indi-
cating that the powders contain mesopores (Type IV).
The BET surface areas of the composites were 201 and
193 m2 g
1, for H3PW12O40/TiO2 and H6P2W18O62/
TiO2, respectively, which increased greatly compared
with the starting polyoxotungstates and the Degussa
P25. Higher specific surface areas of the composites are
benefit for improving their photocatalytic activities.
According to Kumar et al. [29] and Yu et al. [22], forma-
tion of this bimodal pore size distribution is due to hard
aggregates in the powders. There are two types of pores
present in the bimodal pore size distribution. One is the
finer intraaggregated pore, corresponding to micro-
pores, and the other is the larger interaggregated pore,
corresponding to mesopores. These aggregates occurred
during the composite catalyst preparation process.
3.2. Visible-light photocatalytic testing
Parathion-methyl is a kind of chemically stable
organophosphorus pesticide that is extensively used in
agriculture recently. Therefore, we select it as a model
contaminant to test the visible-light photocatalytic activ-
ity of as-prepared composites. Photooxidation of para-
thion-methyl should be based on the following
reaction (Eq. (3)):
CO2 + H2O + PO3- 2- - ð3Þ
4 + SO4 + NO3
At first, visible-light photodecomposition of an aque-
ous parathion-methyl (50 mg l
1) in the absence of the
photocatalyst was neglectable, i.e., there were no any
changes of the concentrations of it after 4 h visible-light
irradiation. In addition, we also did not find obvious
parathion-methyl degradation after 4 h visible-light irra-
diation of the starting H3PW12O40 and H6P2W18O62 in
homogeneous systems. As for the nanosize anatase
TiO2 prepared in the present work, it totally adsorbed
the reactant molecules during the course of mixing it
with an aqueous parathion-methyl in the dark. There-
fore, the parathion-methyl in this system was not de-
tected at the beginning of the photocatalytic reaction.
However, after visible-light irradiation of the suspension
of TiO2 and the reactant exceeded 40 min, the concen-
tration of the reactant increased slowly. The reason
may be desorption of the parathion-methyl from TiO2
as the reaction carrying on. We further tested the visi-
ble-light photocatalytic activity of the commercial avail-
 L. Li et al. / Microporous and Mesoporous Materials 87 (2005) 1–9 7

140 1.0
A
-1

b
Volumme Adsorbed/cm g
120
3

0.8
100 a
H6P2W18 O62/TiO2
80 0.6 H3PW12 O40 /TiO2

Ct /C0
H3PW12 O40
60 H6P2W18 O62
0.4 TiO2
Deguss P25
40
BET surface area of H3PW12O40/TiO2:201 m2g-1 0.2
20
BET surface area of H6P2W18O62/TiO2:193 m2g-1
0 0.0
0.0 0.2 0.4 0.6 0.8 1.0
-30 -20 -10 0 10 20 30 40
Relative Pressure/P/P0
Time (min)
Fig. 7. Photocatalytic degradation of an aqueous parathion-methyl
150
B (C0 = 50 mg l
1) under visible-light excitation. Each photocatalyst
Volume Adsorbed/cm /g

used here was 0.2 g, and Ct refers to the concentration of parathion-

3

120 methyl in the reaction system at t time.

90
The above results are summarized in Fig. 7, and the
60 reaction was performed in the presence of dioxygen dis-
solved in the system from air. Once the reaction was
30 done under an Ar inert atmosphere, neither H3PW12-
O40/TiO2 nor H6P2W18O62/TiO2 exhibited efficient pho-
0 tocatalytic activity to the parathion-methyl degradation.
0 5 10 15 20 At this system, the surface of the catalyst became blue.
Thickness-Harkins & Jura/A The blue composites were analyzed by a UV/DRS
immediately, and a new peak appeared at 750 nm for
2.0 H3PW12O40/TiO2 and 768 nm for H6P2W18O62/TiO2,
b
C was detected respectively, attributed to the interva-
-1

a
Pore volume/cm g

1.6 lence electron transfer (IVCT) occurred in the one-elec-

3

tron reduction product (PW12 O4
7

1.2
0.8
0.4
0.0
0 2 4 6
Pore diameter/nm
Fig. 6. (A) Nitrogen adsorption–desorption isotherms, (B) t-plot of
the H3PW12O40/TiO2, and (C) BJH pore size distributions for
mesopores. a—H3PW12O40/TiO2, b—H6P2W18O62/TiO2.
able photocatalyst, Degassa P-25, to the parathion-
methyl decomposition. It indicated that the photocata-
lytic activity of P-25 was low at this system. Only did
H3PW12O40/TiO2 and H6P2W18O62/TiO2 exhibit obvi-
ous visible-light photocatalytic activity to the degrada-
tion of an aqueous parathion-methyl. That is, the
concentration of the parathion-methyl in the reaction
system decreased rapidly by using H3PW12O40/TiO2 or
H6P2W18O62/TiO2 as the visible-light-driven-photocata-
lyst, and it only needed 40 min to completely destruct it.
40 or P2 W18 O62 ) of
PW12 O40 , or P2 W18 O62 [27]. Formation of PW12 O4

3
6

40
or P2 W18 O7
62 is due to the electron transfer from TiO2
to PW12 O3
6
4

40 or P2 W18 O62 , while PW12 O40 or P2 W18 -
7

O62 was photoinactive. When the reaction was per-
formed in the presence of dioxygen, the blue composite
should yield, however, it was difficult to detect the
absorption peak originated from the blue composite
8 10 by UV/DRS since it can be reoxidized rapidly.
Disappearance of the parathion-methyl in the reac-
tion system does not mean its complete degradation.
From the HPLC effluent curves we found some new
peaks appeared after the peak corresponding to the
parathion-methyl disappeared, suggesting that minerali-
zation of the parathion-methyl required a reaction time
longer than for its degradation due to the successive
breaking of P–O, P=S, N–O, C–C, and C–O bonds.
Some intermediates including acetic acid and formic
acid were detected by IC, and total disappearance of
acetic acid and formic acid needed 120, and 160 min,
respectively, when H3PW12O40/TiO2 was used as a
photocatalyst. The final products yielded during
photodegradation of the parathion-methyl should be
NO
2
3

3 , SO4 , and PO4 , respectively, but only NO3 and


2

SO4 ions were detected with IC. This may be due to
8 L. Li et al. / Microporous and Mesoporous Materials 87 (2005) 1–9
the fact that highly charged PO3
4 ion strongly adsorbed
on the surface of the nanoscale photocatalyst. This
adsorption also led us to hardly determine the concen-
tration of NO
3 or SO4
2

ion quantitatively and accu-
rately, and the estimated yield for NO
2

3 and SO4 ion
was approximately 88% and 71%, respectively.
After the reaction, the catalysts can be easily recov-
ered by sedimentation, and the recovered catalysts were
treated with hot water (80 °C) and ethanol successively
by stirring the suspension vigorously for 3 h. The ob-
tained dried catalysts were analyzed by ICP-AES
XRD, and UV–vis. The loading of the H3PW12O40 or
H6P2W18O62 maintained almost unchangeable, and the
structures of the catalysts were not destroyed. In addi-
tion, after five catalytic recycling, the leakage of
H3PW12O40 or H6P2W18O62 from TiO2 support was less
than 1.5%, and deactivation of the catalysts was hardly
observed. These results further implied that the interac-
tion between the Keggin or Dawson unit and TiO2 sup-
port is indeed chemical rather than physical.
Here, although as-prepared two composites exhibited
main absorption in the range from 200 to 420 nm, fol-
lowing factors ensure their efficient photocatalytic activ-
ity to aqueous parathion-methyl degradation. (i) The
porous structure of the composites. Compared with
the starting POM or TiO2, as-prepared porous POM/
TiO2 composites showed relatively high BET surface
areas, which resulted in an increase in their photocata-
lytic activity by providing more contact areas between
the catalyst and the substrate for the surface-mediated
electron transfer reactions to take place. In addition,
the porous catalysts showed a strong adsorption to the
substrates, which also played an important role to im-
prove their photocatalytic activity since the adsorption
is the first step of the photocatalytic reaction. From
Fig. 7 we observed that the concentration of the para-
thion-methyl decreased by 10% after 30 min adsorption.
Another function for the porous materials is that it pro-
vides enhanced mass transport for the reactant mole-
cules into and out of the pore. (ii) Synergistic effect
existed between the POM unit and the anatase TiO2.
Both H3PW12O40and H6P2W18O62 are effect electron
acceptors in TiO2 photocatalytic systems, and they acted
as the electron shuttles in visible-light illuminating TiO2
[21,22], i.e., POM can accept e
cb from the surface of
TiO2 and form the reduced POM (PW12 O4
40 or
P2 W18 O7

62 ), and the reduced POM was reoxidized by
O2 to yield superoxides (O2
) and its oxidized form for
another catalytic cycle. Therefore, the role of the POM
in TiO2 photocatalysis is critical in enhancing the overall
photoefficiency by retarding the fast recombination of
charge-pair (h+–e
) on TiO2 and produce strong oxi-
dant, O2
. The presence of POMs enhances the genera-
tion of O2
, a kind of main oxidant of parathron-methyl
except OH radicals [20]. The process is described in Eqs.
(4)–(8).
þ
TiO2 þ hm ! e
cb þ hvb ð4Þ
POM þ e


cb ! POM ð5Þ
POM
þ O ! O
þ POM ð6Þ
2 2
O2 þ e
! O2
ð7Þ
cb
hþ  þ
vb þ H2 O ! OH þ H ð8Þ
Thus, the rate of oxidation of parathron-methyl in-
creased significantly under visible-light irradiation of
H3PW12O40 or H6P2W18O62-containing anatase com-
posites. As for the homogeneous H3PW12O40 or
H6P2W18O62, it seems that the concentration of superox-
ides generated is much smaller than that in a heteroge-
neous H3PW12O40/TiO2 or H6P2W18O62/TiO2 system.
When the reaction was performed in an Ar atmosphere,
the stable and photoinactive POM
was formed, and it
was hardly reoxidized in this inert environment, result-
ing in the cessation of the parathron-methyl degradation
reaction. (iii) Relatively narrow band gap of the com-
posite. After formation of the POM/TiO2 composites,
their band gap decreased compared to that with either
the starting POM or the anatase TiO2. Therefore, the
energy of the transition from the valence band to the
doping energy level or from the doping energy level to
the conduction band level was lower than that of the va-
lence band to the conduction band of TiO2. Thus, it is
possible to utilize visible-light type excitation more effi-
ciently than classic Ti-only based one [28].
4. Conclusions
Two efficient heterogeneous photocatalysts, H3PW12-
O40/TiO2, and H6P2W18O62/TiO2, with anatase crystal-
line phase, dual-pore structures, narrow band gap, and
nanometer sizes, were prepared by combination of the
methods of sol–gel and hydrothermal treatment at a
lower temperature (200 °C, 2 °C/min). The design idea
was motivated by the electron transfer mediating ability
of POM, therefore, the role of the POM in TiO2 photo-
catalysis is critical in enhancing the overall photoeffi-
ciency by retarding the fast recombination of charge-
pair (h+–e
) on TiO2 and producing superoxides.
Results of XRD, 31P MAS NMR, Raman scattering
spectroscopy, and UV/DRS indicated that the primary
Keggin or Dawson structure remained intact after
immobilization of them into TiO2 network, which was
ensured by the lower temperature preparation process.
At the same time, the hydrogen bonding and acid–base
interactions existed in the composites. As-prepared
composites were successfully used in the process of
visible-light photocatalytic degradation of an aqueous
parathion-methyl, attributed to the synergistic effect
between the POM and the anatase TiO2, the porous
structures and narrow band gap of the composites.
The above composite catalysts also had the advantages
 L. Li et al. / Microporous and Mesoporous Materials 87 (2005) 1–9
of easily being separated and recovered, and deactiva-
tion of the catalysts was hardly observed after five cata-
lytic recycling.
Acknowledgement
We thank to Professor Y. Liu and Professor C. Shao
for helping determination and explanation the Raman
spectra. Also, the NSFC is acknowledged for financial
support (No. 20271007, 20271045, and 20331010). This
work is also supported by the Program of New Century
Excellent Talents in University (NCET-04-0311).
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