DOI: 10.1002/cssc.
200900100
Titania Nanocrystals and Adsorptive Nanoporous Polymer
Composites: An Enrichment and Degradation System
Yonglai Zhang,[a] Shu Wei,[a] Wei Zhang,[b] Yi-Jun Xu,[b] Sen Liu,[a] Dang Sheng Su,*[b] and
Feng-Shou Xiao*[a]
Composites of titania nanocrystals and adsorptive nanoporous
polymers are synthesized via a two-step solvothermal pathway.
These composites are developed as bifunctional materials for
both the adsorption of organic compounds and photocatalysis,
providing an enrichment and degradation system for the re-
moval of environmental pollutants. The anatase-phase titania
nanoparticles are homogeneously dispersed in the matrix of
Introduction
In recent years, protection of the environment has become a
significant issue in sustainable chemistry. Therefore, considera-
ble efforts have been devoted towards investigating various
adsorbents for treating toxic pollutants in air and water. Gener-
ally, nanoporous polymer and carbon materials can act as effi-
cient absorbents and could be used to solve environmental
problems.[1–7] Porous polymer materials show high adsorptive
capacities for organic compounds owing to their oleophilic
frameworks.[1] They differ from inorganic porous materials,
which can be regenerated by simple calcinations; porous poly-
mer and carbon materials can be reused only after using a
proper method to desorb the adsorbed pollutants, which
strongly impedes their industrial applications. An ideal adsorb-
ent would decompose pollutants and self-regenerate for recy-
cling use. On the other hand, photocatalytic degradation of or-
ganic pollutants is also a fascinating solution to environmental
problems.[8–15] However, the low frequency of collision between
photocatalysts and organic pollutants lowers the reaction rate
of mineralization. Furthermore, secondary pollution caused by
the byproducts produced during the photocatalytic process
also limits the practical applications of photocatalysts.
A promising way to overcome the disadvantages of both ad-
sorbents and photocatalysts is to combine their respective ad-
vantages in a controlled fashion. Some pioneering works, for
example, the loading of TiO2 particles onto various adsorbents
(activated carbon, zeolite, Al2O3, mesoporous silicate, and natu-
ral clay),[16–23] the synthesis of mesoporous titania,[24–29] the fab-
rication of mesoporous TiO2/SiO2 and TiO2/C composites,[30–34]
and the synthesis of porous polymers as photocatalysts,[5] have
been reported. The as-obtained materials revealed improved
properties for both the adsorption and photodegradation of
organic pollutants. An evaluation of the adsorptive properties
of these bifunctional materials, however, is still lacking. Thus, it
is a challenge to develop highly efficient adsorptive materials
containing excellent photocatalytic activities.
ChemSusChem 2009, 2, 867 – 872  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
the nanoporous polymers. The composites exhibit nanoporous
structures, high surface areas, and excellent stabilities. Experi-
mental results show that the composites have excellent ad-
sorptive properties for organic compounds in water and air
and high photocatalytic activities under UV irradiation. These
bifunctional materials may have promising applications in envi-
ronmental protection.
Herein, we report the first in situ synthesis of titania nano-
crystals and nanoporous polydivinylbenzene (PDVB) compo-
sites. These composites are efficient bifunctional materials for
the adsorption of organic compounds and photocatalytic deg-
radation.
Results and Discussion
Synthesis
Titania nanocrystals and nanoporous polymer composites were
synthesized via a two-step solvothermal pathway (Figure 1).
Here, solvothermal polymerization was considered a facile
method for the preparation of nanoporous polydivinylbenzene
(PDVB) containing a loose network.[35] Divinylbenzene mono-
mers were polymerized in the presence of THF and tetrabutyl
titanate (TBT) in the first solvothermal treatment. After the in-
troduction of a desired amount of water, TBT was hydrolyzed,
forming amorphous titania nanoparticles in the confined space
of the polymeric skeleton. After a second solvothermal treat-
ment, nanocrystals of titania were formed and homogeneously
dispersed in the system. Finally, titania nanocrystals and nano-
[a] Y. Zhang, S. Wei, S. Liu, Prof. F.-S. Xiao
College of Chemistry and
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry
Jilin University
Qianjin Street 2699, Changchun 130012 (PR China)
Fax: (+ 86) 431 85168624
E-mail: fsxiao@mail.jlu.edu.cn
[b] Dr. W. Zhang, Dr. Y.-J. Xu, Dr. D. S. Su
Department of Inorganic Chemistry
Fritz Haber Institute of the Max Planck Society
Faradayweg 4–6, 14195 Berlin (Germany)
E-mail: dangsheng@fhi-berlin.mpg.de
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/cssc.200900100.
867
 D. S. Su, F.-S. Xiao et al.

Table 1. Physicochemical properties of titania nanoparticles and nanopo-

rous polymer composites prepared under different conditions.

Sample TiO2 content [wt %] SBET Vp dp

TGA[a] Mass reduction[b] ACHTUNGRE[m2 g 1] ACHTUNGRE[cm3 g 1] [nm]
P-T-0.25 – 5.7 651 0.88 9.3
P-T-0.5 – 9.8 617 0.89 9.2
P-T-1 16.4 17.2 543 1.03 11.4
P-T-2 30.6 31.0 500 0.94 11.8
P-T-3 45.2 45.8 424 1.04 22.1
P-T-4 – 47.8 354 1.13 25.4
P-T-1[c] – – 484 1.02 11.8

[a] Results calculated from thermogravimetric analysis (TGA). [b] Results

Figure 1. Synthesis of titania nanocrystals and nanoporous polymer compo- calculated from mass reduction after calcination at 650 8C for 3 h. [c] Sam-
sites. TBT: tetrabutyl titanate; (P)DVB: (poly)divinylbenzene ples exposed to UV irradiation (125 W) for 7 d. SBET: Brunauer–Emmett–
Teller surface area; Vp : total pore volume; dp : average pore diameter.

porous polymer composites were obtained after evaporation

of the solvents (THF, water, and n-butanol, generated from the
hydrolysis of TBT). The samples are labeled as P-T-x, where x
stands for the mass ratio of TBT to DVB in the starting solu-
tions.

Characterization of the samples

Nitrogen adsorption–desorption isotherms and pore size distri-
bution curves of the P-T-x samples (x = 0.25–4) are shown in
Figure 2. The P-T-0.25 sample showed a typical type IV iso-
therm with a hysteresis loop (P/P0 at 0.7–0.9, Figure 2 a, curve
A), indicating a meso-structured composite. Correspondingly,
the pore size, calculated from the desorption curve, is 9.3 nm.
Composites with different TiO2 content also showed nitrogen
uptakes (P/P0 at 0.7–1.0), giving surface areas of 354–
651 m2 g 1 and pore sizes of 9.2–25.4 nm (Table 1).
Figure 3 shows the wide-angle X-ray diffraction (XRD) pat-
terns of the P-T-x samples, showing the predominant anatase
phase (2q = 25.38, 38.08, 48.08, 55.08, 62.68, 68.78, and 75.08,
Figure 2. a) N2 adsorption–desorption isotherms and b) pore size distribution
curves of (A) P-T-0.25, (B) P-T-0.5, (C) P-T-1, (D) P-T-2, (E) P-T-3, and (F) P-T-4.
The isotherms of B–F have been offset by 300, 600, 900, 1200, and
1500 cm3 g 1, respectively, along the vertical axis for clarity. The pore size dis-
tribution curves of B–F have been offset by 1.5, 3, 4.5, 6, and 7.5 cm3 g 1, re-
spectively, and each of them was estimated by the Barrett–Joyner–Halenda
model from a desorption branch of the isotherm.
Figure 3. Wide-angle XRD patterns of (A) P-T-0.25, (B) P-T-0.5, (C) P-T-1, (D) P-
T-2, (E) P-T-3, and (F) P-T-4 (solid squares: anatase; solid triangle: brookite).
solid squares). A small amount of brookite phase (2q = 30.88,
solid triangle) was present in all samples. The broad peak be-
tween 108 and 308 corresponds to the amorphous polymeric
framework.
The morphology and porosity of the composites were char-
acterized by scanning electron microscopy (SEM). As typical ex-
amples, SEM images and energy-dispersive X-ray (EDX) spectra
of P-T-1 and P-T-3 are shown in Figure 4. The P-T-1 composite
showed a monolithic morphology (inset of Figure 4 a). The
high-magnification image shows that P-T-1 is highly porous,
with a pore size in the mesopore range (Figure 4 b). The P-T-3
composite shows characteristics similar to P-T-1 except for the
presence of large cavities in the macropore range (Figure 4 d
and e). The EDX spectra (Figure 4 c and f) only shows the pres-
ence of carbon, oxygen, and titanium in the samples. Quantita-
tive results revealed that the atomic ratio of oxygen to titani-
um is close to the ideal value of 2. In addition, the two sam-
ples showed different Ti-Ka,b and O–K content (Figure 4 c and
f), in agreement with the titania content shown in Table 1.
Figure 5 shows the microstructure investigations for P-T-3.
Titania nanoparticles with an average diameter of 10 nm uni-
formly dispersed in the PDVB framework. Only carbon, titani-

868 www.chemsuschem.org  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ChemSusChem 2009, 2, 867 – 872
Titania Nanocrystals and Adsorptive Nanoporous Polymer Composites

The scanning transmission elec-

tron microscopy (STEM) images
in Figure 5 c show that titanium,
oxygen, and carbon are homo-
geneously distributed in the
composite materials.
Figure 6 shows the UV/vis
spectra of P-T-1 and P-T-3 as well
as the commercially available
photocatalyst P25 for compari-
son. A significant increase in the
absorption at wavelengths
below 410 nm can be assigned
to the intrinsic band gap absorp-
tion of anatase and rutile TiO2
for P25. The absorption edge
shifts towards shorter wave-
lengths for P-T-1 and P-T-3 sam-
ples (380 nm) owing to the band
gap absorption of anatase and
brookite TiO2 (Figure 3).[36] The
slight absorption band for P-T-1
between 380 and 500 nm can
be assigned to the absorption of
PDVB.

Stabilities of the samples

The thermal stability of the com-
posites was investigated by ther-
mogravimetric analysis (TGA).
Figure 7 a shows a significant
Figure 4. a,b) SEM images, and c) EDX spectra of P-T-1; d,e) SEM images, and f) EDX spectra of P-T-3. mass loss starting at 370 8C for
P-T-1. This is much higher than
pure PDVB (ca. 270 8C), which
um, and oxygen were detected (see the electron energy loss
spectroscopy (EELS) spectrum, inset of Figure 5a), indicating
the presence of polymers and titania, consistent with the EDX
spectroscopy results. Figure 5 b shows highly crystallized titania
nanoparticles. It is known that anatase titania (space group =
I41/amd) has lattice parameters of a = b = 3.78 , c = 9.51 ,
and a = b = g = 908 (see inset of Figure 5b). In the high-resolu-
tion transmission electron microscopy (HRTEM) image, the lat-
tices of the (101) and (011) planes of anatase titania were iden-
tified and their interplanar spacings are 0.35 nm. The diameter
of the particles is ca. 10 nm, as indicated by the circled area.
Between the particles is amorphous PDVB. Similar observations
were made for the P-T-x samples with various titania content.
As shown in the Supporting Information, titania nanoparticles
with diameters of 5–10 nm homogeneously distributed in the
P-T-0.5 and P-T-1 samples (see HRTEM images). It is worth
noting that the size of the titania nanoparticles does not line-
arly increase in proportion to the titania content. No large tita- Figure 5. a) Transmission electron microscopy (TEM), and b) high-resolution
(HR)TEM images of P-T-3; the inset in (a) is the EELS spectrum; the inset in
nia particles were found even though the TiO2 content was
(b) is the crystallography model of anatase titania where Ti atoms are in
very high (ca. 45 % for P-T-3, Table 1) because the PDVB net- white and O atoms are in gray; c) single (S)TEM image, Ti, O, and C elemen-
work hindered the agglomeration of the titania nanoparticles. tal maps of the sample (from left to right).

ChemSusChem 2009, 2, 867 – 872  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemsuschem.org 869

Figure 6. UV/vis spectra of P-T-1, P-T-3, and P25.
was prepared as a comparable sample, indicating that the in-
troduction of titania into the PDVB framework greatly im-
proves the thermal stability of the composites. In addition, the
P-T-1 sample gave a large mass loss (83.6 %), indicating a tita-
nia content of 16.4 %. When the titania content was increased,
mass loss for the P-T-2 and P-T-3 samples started at 385 and
410 8C, respectively, further confirming the effect of titania on
the thermal stability of the composites. The P-T-2 and P-T-3
samples gave relatively small mass losses (69.4 and 54.8 %, re-
spectively) owing to the high titania content. The titania con-
tent calculated from the TGA curves is similar to that calculat-
ed from mass loss after calcination at 650 8C for 3 h in air
(Table 1). The stability of these samples under UV irradiation
was also evaluated by exposing the P-T-1 composite to UV irra-
diation (125 W) for 7 days. As shown in Figure 7 b , the P-T-1
sample shows similar nitrogen adsorption isotherms and pore
size distribution curves before and after UV irradiation for
7 days, indicating the excellent stability of the porous struc-
ture. The FTIR spectra (see Supporting Information) further
confirmed the high stability. For example, after irradiation for 7
days, the IR spectrum of P-T-1 did not change.
Adsorptive properties and photocatalytic activities
The adsorptive properties and photocatalytic activities of the
composites were evaluated by a two-step procedure and com-
pared with P25 and Amberlite XAD-4 adsorptive resin (Fig-
ure 8 a). Rhodamine-B (RhB) was chosen as a probing pollutant
for both adsorption and photocatalytic experiments. Firstly, an
adsorptive procedure was performed in the dark for 180 min.
Both P-T-1 and P-T-3 samples showed similarly high adsorptive
capacity and adsorptive rate. More than 68 % of RhB in the
aqueous solution was adsorbed by the P-T-1 sample (65 % for
P-T-3). Following adsorption for 180 min, the adsorptive capaci-
ty reaches saturation. On the contrary, P25 showed negligible
adsorption owing to the low specific surface area (ca.
45 m2 g 1). The XAD-4 resin showed a relatively low adsorptive
rate and nearly 25 % of RhB was adsorbed after 180 min. The
P-T-1 and XAD-4 samples with large BET surface areas (543 and
870 www.chemsuschem.org  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
D. S. Su, F.-S. Xiao et al.
Figure 7. a) TGA curves of P-T-1, P-T-2, P-T-3, and pure PDVB. b) N2 isotherms
and pore size distribution curves of P-T-1 before and after exposure to UV ir-
radiation (125 W) for 7 d. Isotherm and pore size distribution curves have
been offset by 200 cm3 g 1 and 1.5 cm3 g 1, respectively, along the vertical
axis for clarity.
750 m2 g 1, respectively) showed relatively low adsorptive rates
compared with the P-T-3 sample (424 m2 g 1). This phenomen-
on is possibly owing to the different hydrophobicities of the
samples. In the second step, the mixture was exposed to UV ir-
radiation for a further 180 min. Interestingly, an abrupt de-
crease in the concentration of the RhB solutions was observed
after the saturated adsorption for the P-T-1 and P-T-3 samples
under UV irradiation, which is assigned to the photocatalytic
degradation of the RhB adsorbed by the composite materials
and the re-adsorption of the RhB in the solution. In addition,
the decrease in concentration for P-T-3 (45.8 % titania) is more
obvious than that of P-T-1 (17.2 % titania), owing to the rich-
ness of titania in the P-T-3 sample. The P25 sample also gave
an abrupt decrease in concentration owing to its photocatalyt-
ic decomposition. On the contrary, the XAD-4 resin did not
show an abrupt decrease in concentration because of the ab-
sence of photocatalytic activity. The P-T-1 and P-T-3 samples
showed superior adsorptive properties and good photocatalyt-
ic activities compared to the P25 and XAD-4 samples. The P25
sample only exhibited photocatalytic activity without any ad-
ChemSusChem 2009, 2, 867 – 872
Titania Nanocrystals and Adsorptive Nanoporous Polymer Composites
Figure 8. a) Concentration change of RhB solutions under adsorptive (black
line) and photocatalytic (blue line) processes over P-T-1, P-T-3, P25, and
XAD-4 resin, respectively. b) Concentration change of RhB solutions under
adsorptive and photocatalytic process over P-T-3 sample. (Content of RhB
adsorbed in P-T-3 during photocatalytic process was evaluated by extracting
RhB from the hybrid of RhB and P-T-3 in ethanol. Inset: absorption change
of extracted RhB in ethanol).
sorptive abilities; whereas XAD-4 exhibited general adsorptive
properties without photocatalytic activity. Thus, our compo-
sites combining adsorptive and photocatalytic properties are
much more efficient for treating pollutions in aqueous solu-
tions than single photocatalysts or adsorbents.
To identify the photocatalytic activity for the RhB adsorbed
in the composite materials after full adsorption, the hybrids of
P-T-3 and RhB with different photodegradation times were ex-
tracted into ethanol, respectively. The concentration change of
RhB in ethanol represents the content change of the adsor-
bate. As shown in Figure 8 b, the RhB solution (20 ppm) was
fully adsorbed by the P-T-3 sample after 60 min in the dark.
The mixture was then exposed to UV irradiation and the pho-
tocatalytic degradation of the RhB adsorbed in the P-T-3
sample occurred. The concentration of RhB extracted into the
ethanol showed a significant decrease owing to the photocata-
lytic decomposition of RhB. Most of the RhB decomposed fol-
lowing UV irradiation for 180 min. The slight residue was de-
rived from the adsorbed RhB molecules in the polymeric
ChemSusChem 2009, 2, 867 – 872  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
matrix, which lacks titania nanoparticles. Particularly, the aque-
ous solution remained clear during UV irradiation, indicating
no desorption of RhB.
The gas phase adsorptive properties were tested using ace-
tone and water as probing molecules (Figure 9). Interestingly,
all of the composites showed large adsorptive capacities for
Figure 9. Adsorptive capacity of acetone and water as probing molecules in
gas phase over P-T-x (x = 0.25–4) and XAD-4.
acetone (1.24–0.60 g g 1). Compared with the adsorptive resin
XAD-4, the P-T-0.25 and P-T-0.5 samples gave higher adsorp-
tive capacities, indicating superior adsorptive properties. A fur-
ther increase in the titania content (P-T-x, x = 1–4) resulted in
the decrease of adsorptive capacity for acetone, which is at-
tributed to the decrease in polymer content and BET surface
area. On the contrary, the adsorptive capacity for water in-
creased with the titania content owing to the decrease in hy-
drophobicity. Generally, the organic framework and the porous
structure are favorable for the formation of hydrophobic surfa-
ces.[37, 38] As a result, a larger organic polymer content contrib-
utes to a higher hydrophobicity. The XAD-4 resin also shows
significant hydrophobicity and this feature might explain the
low adsorptive rate for the XAD-4 resin. The high adsorptive
capacity for organic compounds in the gas phase indicates the
potential use of these composite materials for the enrichment
and degradation of volatile organic compounds.
Conclusions
Titania nanocrystals and nanoporous adsorptive polymer com-
posites have been prepared by a two-step solvothermal path-
way. These composites were developed as bifunctional materi-
als for both adsorption and photocatalysis, and designed as an
enrichment and degradation system for the elimination of en-
vironmental pollutants. Experimental results show that these
composites exhibit excellent adsorptive properties and high
photocatalytic activities. The bifunctional materials could po-
tentially be used in the decontamination of organic pollutants
from water and the atmosphere.
www.chemsuschem.org 871

Experimental Section
DVB was purchased from Tianjin-Guangfu Chemical Corp., and THF,
azobisisobutyronitrile (AIBN), TBT, and acetone were purchased
from Beijing Chemical Corp. Amberlite XAD-4 resin was purchased
from Aldrich. P25 was purchased from Degussa Co. All chemicals
were used as-received.
In a typical synthesis of titania nanocrystals and adsorptive nano-
porous polymer composites, the monomer of DVB (2 g) was dis-
solved in THF (10 mL) containing TBT (y g, y = 0.5–8), and the initia-
tor AIBN (0.05 g) was added. After stirring for 4 h at RT, the trans-
parent solution was transferred into an autoclave. After solvother-
mal treatment at 100 8C for 24 h, deionized water (10 mL) was
added into the autoclave to hydrolyze the TBT. After another solvo-
thermal treatment at 100 8C for 24 h and 180 8C for 24 h, a solid
monolith was obtained following slow evaporation of the solvents
at RT. The samples were labeled as P-T-x, where x stands for the
mass ratio of TBT to DVB in the starting solutions. A PDVB sample
without addition of titanium was prepared in the same conditions
as the P-T-x samples.
Adsorption and photocatalytic experiments were performed by a
two-step procedure. Typically, the sample (50 mg) was added to an
aqueous solution (50 mL) containing RhB (20 ppm or 100 ppm)
under vigorous stirring. Firstly, the mixture was placed in the dark
for 1 or 3 h to evaluate the adsorptive properties. Then, the solu-
tion was irradiated by a 125 W mercury lamp for another 3 h to
evaluate the photocatalytic activities. The concentration of RhB
was determined at different intervals by UV-vis absorption.
Nitrogen adsorption isotherms were measured with a Micromeritics
Tristar 3000 analyzer at 77 K. Samples were degassed for 10 h at
150 8C before the measurements were recorded. Powder XRD data
were collected on a Rigaku D/MAX 2550 diffractometer with Cu Ka
radiation (l = 1.5418 ). SEM experiments were performed on a Hi-
tachi S4800 (2.0 kV) equipped with EDX detectors. TEM experi-
ments were performed on a Philips CM 200 LaB6 (200 kV) and a
Philips CM200 FEG (200 kV) equipped with EELS. TG analysis was
carried out on a NETZSCH STA 449C with a heating rate of
20 8C min 1 from RT to 800 8C. The concentrations of the RhB solu-
tions were measured by a Shimadzu (UV-2450) UV/vis spectropho-
tometer. Measurements of adsorptive capacity for acetone and
water were estimated from the change in sample weight before
and after exposure of probing vapor to the samples under vacuum
conditions (ca. 1 torr) at RT. Before adsorption, the samples were
evacuated at 120 8C for 3 h to remove adsorbates. FTIR spectra
were performed on a IFS 66 V/S (Bruker) IR spectrometer in the
range 400–4000 cm 1, and the samples were measured until the
final pressure was 4  10 3 mbar.
Acknowledgements
This work was supported by the State Basic Research Project of
China (2009CB623507), the National Natural Science Foundation
of China (20773049), and the PPP. We gratefully acknowledge Dr.
Jian Zhang at the Fritz-Haber-Institute of the Max Planck Society-
for helpful discussions.
Keywords: adsorption · composites · nanoporous materials ·
photochemistry · titanium
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Received: April 22, 2009
Published online on August 31, 2009
ChemSusChem 2009, 2, 867 – 872