1-s2.0-s0169433212007015-main

7/27/2019 1-s2.0-S0169433212007015-main

1/7

Applied Surface Science 258 (2012) 74487454

Contents lists available at SciVerse ScienceDirect

Applied Surface Science

journal homepage: www.elsevier .com/ locate /apsusc

High-temperature hydrothermal synthesis ofcrystalline mesoporous TiO2 with

superior photo catalytic activities

Fujian Liu, Chun-Lin Liu, Baowei Hu, Wei-Ping Kong, Chen-Ze Qi

Institute of Applied Chemistry,Department of Chemistry, Shaoxing University, Shaoxing 312000, Peoples Republic of China

a r t i c l e i n f o

Article history:

Received6 March2012

Receivedin revised form 5 April 2012Accepted 9 April 2012

Available online 21 April 2012

Keywords:

High temperature synthesis

Crystalline mesoporous TiO2Complex bond interaction

Photo catalysis

Recyclability

a b s t r a c t

Mesoporous titanium dioxide with crystalline mesopore walls (M-TiO2-ns) have been successfully syn-

thesized through the self-assembly of poly 4-Vinylpyridine template and tetrabutyl titanate precursor

based on their complex bond interaction under high temperature (180 C) hydrothermalconditions. X-ray

diffraction shows that M-TiO2-ns have highly crystalline mesopore walls with anatase phase characters;

N2 sorptiondesorptionisotherms, SEM and TEM images show that M-TiO2-ns have high BET surface areas

(85 and 120m2/g, respectively), large pore volumes (0.32 and 0.34 cm3/g, respectively) and crystalline

mesopore walls, which exhibit monolithic morphology with crystal sizes around 35m. Interestingly,

M-TiO2-ns exhibit much higher catalytic activities and good recyclability in both induced reduction of

decabromodiphenyl and oxidation ofRhodamine B under UV light than those ofnonporous crystalline

TiO2 and M-TiO2 templated by hydrocarbon surfactant of F127, which is even comparable with that of

commercial P25. Combination ofthe unique characters such as crystallinity, stable mesostructure, large

BET surface areas and superior photo catalytic activities make M-TiO2-ns a kind ofpotentially important

material for removing oforganic pollutions in environment through green photo irradiation processes.

2012 Elsevier B.V. All rights reserved.

1. Introduction

Mesoporous titanium dioxide with crystalline mesopore

walls (M-TiO2) possesses some unique features such as good

photo induced electron transfer, excellent photo catalytic activ-

ities, superior chemical stabilities, low cost and environmental

friendly [121], which results in their potentially important

applications in the fields of photoconductors, sensors, biology

active materials, dye sensitized solar cells and photocata-

lysts [121]. Generally, M-TiO2 was synthesized using nonionic

hydrocarbon surfactants such as poly(oxyethylene) alkyl ether

or poly(oxyethylene)b-poly(oxypropylene)b-poly(oxyethylene)

triblock copolymer (EOnPOmEOn) as structure directing agents

[2226], the synthetic temperature is usually kept below 140 C

due to relative lower thermal stabilities of the surfactant tem-

plates. However, the low synthetic temperature usually results inthe samples with amorphous frameworks. Nevertheless, for effi-

cient performance as functional materials mesoporous TiO2 with

crystalline mesopore walls are more needed because the samples

with amorphous framework will constrain the recombination of

photo-excited electrons and holes [27,28], which is unfavorable for

their wide applications in the fields of solar cells or photo catalysis.

Correspondingauthors. Tel.: +86 575 88345681; fax: +86 575 88345681.

E-mail address: [email protected](C.-Z. Qi).

Generally, the transformation of amorphous TiO2

to crystalline

form such as anatase or rutile usually demands of high temper-

ature (400C) treatment [2931], however the crystallization of

the framework at high temperature usually results in partially

collapse of the mesostructure due to relative high bending force

should be overcome in the processes of crystal units formation

[2224,2832]. Interestingly, under hydrothermal conditions, the

crystallization of mesopore walls could be achieved at relative

lowertemperature (160 C) [33,34]. Very recently,Xiao et al.have

successfully synthesized a series of ordered and stable mesoporous

materials under high temperature (upto 260 C) and hydrothermal

conditions [35,36], which offers great opportunity for synthesis of

M-TiO2 through the high-temperature hydrothermal route.

We demonstrate here a successfully synthesis of M-TiO2-ns

through high temperature (180C) hydrothermalroute, which was

achieved from the self-assembly of poly 4-Vinylpyridine (P4VP)template with Ti precursor of tetrabutyl titanate based on their

complex bond interaction [37]. Interestingly, the resulted M-TiO2-

ns exhibited highly crystalline mesopore walls and large BET

surface areas (85 and 120 m2/g, respectively). Moreover, even

after the removal of template by calcination at high tempera-

ture (550 C), the mesostructure of M-TiO2-ns was intact, and the

accompanied enhanced crystalinity also happened. In contrast, M-

TiO2 templated by hydrocarbon surfactant of F127 (M-TiO2-F127)

or the sample synthesized without using any template (nonporous

TiO2) showed very low BET surface areas (31 and 7m2/g, respec-

tively) and poor porosities. More importantly, M-TiO2-ns exhibited

0169-4332/$ see front matter 2012 Elsevier B.V. All rights reserved.

http://dx.doi.org/10.1016/j.apsusc.2012.04.059
http://localhost/var/www/apps/conversion/tmp/scratch_9/dx.doi.org/10.1016/j.apsusc.2012.04.059http://localhost/var/www/apps/conversion/tmp/scratch_9/dx.doi.org/10.1016/j.apsusc.2012.04.059http://www.sciencedirect.com/science/journal/01694332http://www.elsevier.com/locate/apsuscmailto:[email protected]://localhost/var/www/apps/conversion/tmp/scratch_9/dx.doi.org/10.1016/j.apsusc.2012.04.059http://localhost/var/www/apps/conversion/tmp/scratch_9/dx.doi.org/10.1016/j.apsusc.2012.04.059mailto:[email protected]://www.elsevier.com/locate/apsuschttp://www.sciencedirect.com/science/journal/01694332http://localhost/var/www/apps/conversion/tmp/scratch_9/dx.doi.org/10.1016/j.apsusc.2012.04.059

7/27/2019 1-s2.0-S0169433212007015-main

2/7

F.Liu et al. / AppliedSurface Science258 (2012) 74487454 7449

much higher catalytic activities and good recyclability in both UV

light induced reduction degradation of decabromodiphenyl ether

(BDE209) andoxidation degradation of organic dyeof RhodamineB

(RhB) than those of nonporous TiO2 and M-TiO2-F127, which were

even comparable with that of commercial P25.

2. Experimental

2.1. Chemicals and regents

4-Vinylpyridine, F127 (PEO106PPO70PEO106, molecular

weight of about 12,600), titanium isopropoxide and BDE209 was

purchased from SigmaAldrich Company. Azodiisobutyronitrile

(AIBN) initiator, ethanol, tetrabutyl titanate, RhB were obtained

from Tianjin Guangfu Chemical Reagent. P25 was purchased from

Degussa Co. without any treatment.

2.2. Preparation of the samples

2.2.1. Synthesis of P4VP template

P4VP template was synthesized through the polymerization of

4-Vinylpyridine in the presence of ethanol solvent under refluxing.

As a typical run, 2.0 g of 4-Vinylpyridine monomer was dissolved

into a solution containing 10mLof ethanol and 0.05g of AIBN ini-

tiator, then the mixture was rapidly heated to 80C, after vigorous

stirring for 6h, the P4VP template with molecular weight about

26,000 was obtained.

2.2.2. Synthesis of M-TiO2-ns

M-TiO2-ns (wheren stand for the molar ratio of titanate/P4VP)

were synthesized by self assembly of tetrabutyl titanate with P4VP

templateat roomtemperature,hydrothermallytreatment at 180C

for 24h, and calcination was done at 550 C for 5 h. As a typical

run for synthesis of M-TiO2-195, 2.0g of P4VP template was dis-

solved into 50mLof ethanol, then 15mmol of tetrabutyl titanate

was added into the mixture under vigorous stirring, obviously pre-

cipitate was formed. After the ethanol slowly evaporates at room

temperature under stirring, a brown solid was obtained almostafter 48h. The obtained solid was transferred into an autoclave and

was subjected to hydrothermal treatment at 180C for 48h. Calci-

nation was done at 550 C for 5 h in the air and M-TiO2-195 with

opened mesopores were obtained. In the meanwhile, nonporous

crystalline TiO2 was synthesized under the same condition with

that of M-TiO2-195 without using any template.

2.2.3. Synthesis of M-TiO2-F127

For comparison, crystalline mesoporous TiO2 was synthesized

using hydrocarbon surfactant of F127 as template and it was desig-

nated as M-TiO2-F127, which could be obtained from self assembly

of titanium isopropoxidewith F127 under acid condition. As a typi-

cal run, 2.0 g of F127was dissolved into a mixture containing 76mL

of water and 3.3 mLof HCl (10 M), followed by addition of 40mmolof titanium isopropoxide, after stirring at 40C for 20 h , a gel was

formed, which was immediately transferred into an autoclave for

further condensation at 180 C for another 24h, then the obtained

product was collected by filtration, drying in air, and calcination at

550 C for 5h. M-TiO2-F127 with opened mesopores was obtained.

2.3. Characterizations

X-ray diffraction (XRD) patterns were recorded on Rigaku

D/Max-2550 using nickel-filtered Cu K radiation. Nitrogen

isotherms were measured using a Micromeritics ASAP 2020M

system. The pore-size distribution for mesopores was calculated

using the BarrettJoynerHalenda (BJH) model. The UVvis dif-

fuse reflectance spectra were recorded on a Perkin-Elmer Lambda

10 20 30 40 50 60 70 80

A: anatase

R: rutile

A/RA

Inte

nsity(a.u.) f

e

d

c

b

a

AA/RAA

A

2Theta (degree)

Fig. 1. Wideangle XRDpatterns of (a)as synthesized mesoporous TiO2 synthesized

at 100 C, (b) as synthesized M-TiO2 -195, (c) nonporous TiO2, (d) M-TiO2-F127, (e)

M-TiO2-390 and(f) M-TiO2-195.

20 UV/vis spectrometer. Transmission electron microscopy (TEM)

experiments were performed on a JEM-3010 electron microscope

(JEOL, Japan) with an acceleration voltage of 300 kV. SEM imageswere performed on JSM-6700F electron microscopes. XPS spectra

were performed on a Thermo ESCALAB 250 with Al K radiation,

andbindingenergieswerecalibratedusingthe C1speakat 284.9eV.

Thermogravimetric analysis (TG) was performedon a Perkin-Elmer

TGA7 and a DTA-1700 in flowing air.

2.4. Catalytic test

2.4.1. Photo reduction

UV light induced photo catalytic reduction of BDE209 was car-

ried out in a cylindrical glass under irradiation by a PLS-SXE300

300 W xenon lamp equipped with a 360 n m cutoff filter. As a

typical run, 5.0 mg of catalyst was added into a cylindrical glass

containing 5 mL of BDE209 solution with the concentration of2105 mol/L,followed by addition of certain content of isopropyl

alcohol (0.33 mol/L) as the electron donor. Before irradiation, the

mixture was stirring for30 minandsonicated for1 minunderdark-

ness, then the Pyrex vessel was purged with argon for 30min for

removing of oxygen. At a given time interval of irradiation, small

aliquots were withdrawn and analyzed using Shimadzu HPLC sys-

tem (LC-20AT pump and UV/vis SPD-20A detector).

2.4.2. Photo oxidation

UV light induced photo catalytic oxidation of RhB was also car-

ried out in a cylindrical glass under irradiation by a PLS-SXE300

300 W xenon lamp. As a typical run, 50.0mg of catalyst was added

into a cylindrical glass containing 50mLof RhB solution with the

concentration of 40ppm. Before irradiation, the mixture was stir-ring under darkness for 30min until the sorption was achieved

equilibrium. At a given time interval of irradiation, small aliquots

were withdrawn, filtered and analyzed by UV spectroscopy.

3. Results and discussion

3.1. Structural characterizations

3.1.1. XRD

Fig.1 shows theXRD patterns of various samples. Forthe as syn-

thesized M-TiO2-195, a series of obvious broad peaks associated to

anatase phase could be clearly seen [9], indicating the formation

of TiO2 nanocrystals under high-temperature hydrothermal con-

ditions (Fig. 1b). In contrast, the mesoporous TiO2 synthesized at

7/27/2019 1-s2.0-S0169433212007015-main

3/7

7450 F. Liu et al. / Applied Surface Science258 (2012) 74487454

0.0 0.2 0.4 0.6 0.8 1.00

40

80

120

160

200

240

d

c

Volumeadsorptio

n(cm

3/g)

a

b

Relative pressure (p/p )0

200 40 60 80 100-0.1

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

d

c

dV/dlogD(cm

3/g)

Pore diameter (nm)

a

b

Fig. 2. N2

isothermals andpore size distribution of (a) M-TiO2

-195, (b)M-TiO2

-390, (c) M-TiO2

-F127 and(d) nonporousTiO2

.

relative lower temperature (100 C) exhibited amorphous meso-

pore walls (Fig. 1a). Notably, after remove of the template by

calcination at 550 C, the diffractions of all the samples became

more narrow and resolved, indicating further growth and size

increasing of TiO2 nanocrystals (Fig. 1f) [38,39], similar results

could also be found in thesamples of M-TiO2-F127 andM-TiO2-390

(Fig. 1d and e). In addition, the sample synthesized without using

any template gave a series of relative broad peaks (Fig. 1c), which

may be attributed to the smaller titanium dioxide nanocrystals

formed underhigh temperature hydrothermal conditions. Notably,

the crystalline mesopore wallswould result in theirgood structural

stability and good photo catalytic properties.

3.1.2. N2 sorption isotherms

Fig. 2 shows the N2 sorptiondesorption isotherms and the cor-

respondingly pore size distribution over various samples. Notably,

M-TiO2-195 and M-TiO2-390 showed typical IV isotherms, giving

a sharp capillary condensation step at P/P0 of 0.700.90, indicating

Fig. 3. SEMimages of M-TiO2-195.

7/27/2019 1-s2.0-S0169433212007015-main

4/7


Fig. 4. TEM imagesof (a) and (b) M-TiO2-390, and (c) and (d) M-TiO2-195.

thepresenceof obviouslymesostructure in thesamples (Fig.2a and

b), which gave high BET surface areas (85 and 120m2/g respec-

tively, Table 1) and uniform pore diameter around 1214nm

(Fig. 2a and b, Table 1). Obviously, the BET surface areas of M-

TiO2-ns were much higher than that of commercial P25 (45m2/g),

which was a kind of typical UV light induced photo catalyst

extensively used in industry [40]. In contrast, M-TiO2-F127 and

nonporous TiO2 showed nearly no mesostructure, giving very

low BET surface areas (31 and 7 m2

/g) and pore volumes (0.18and 0.04cm3/g, Fig. 2c and Table 1). Interestingly, the BET surface

area of the obtained samples increased with the content of P4VP

template increasing. For example, M-TiO2-195 showed the surface

area at 120 m2/g, which was higher than that of M-TiO2-390

Table 1

The textural parameters of various samples.

Run Samples SBET (m2/g) Vp (cm

3 /g) Dp (nm)c

1 M-TiO2 120 0.34 11.9

2 M-TiO2 85 0.32 14.4

3 M-TiO2-F127 31 0.18 28.5

4 Nonporous TiO2 7 0.04

5 P25 45 0.17

(85m2/g, Table 1), indicating the higher content of P4VP tem-

plate was favorable for obtaining the samples with abundant

mesoporosity.

3.1.3. Electronic microscope images

Fig. 3 shows the SEM images of M-TiO2-ns, which exhibited

monolithic morphology with the crystal sizes around 35m

(Fig. 3a). High resolved SEM images showed that the sample exhib-

ited poroussurface with theporesize around1015 nm,suggestingtheir abundant nanoporosity. Fig. 4 shows the TEM images of M-

TiO2-ns, which exhibited wormhole like mesopores with pore size

around 1214nm, in good agreement with the results obtained

from N2 isothermals and SEM. High-resolved TEM image (Fig. 3d)

of M-TiO2-195 clearly showed several nanocrystallites with well-

defined lattice planes, crossing through the mesopores, suggesting

the highly crystalline mesopore walls, in good agreement with

XRD results. Notably, the mesoporoses in M-TiO2-195 could be

form by the aggregation of nanosized TiO2 crystals, which was

quite different from the samples formed by simply aggregation

of nanoparticles due to strong interaction between Ti species

and P4VP template, which resulted in the sample with stable

mesostructure, similar results have also been reported previously

[41].

7/27/2019 1-s2.0-S0169433212007015-main

5/7


100 200 300 400 500 600 700 8000.20.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

TG(%)

Temperature ( C)

Fig. 5. TG curve of as synthesized M-TiO2-195.

3.1.4. Thermal analysis

Fig. 5 shows the TG curve of as synthesized M-TiO2-195. Clearly,

M-TiO2-195had a weight loss of32% centered at420C, which was

resulted from the decomposition of P4VP template in the sample.Apparently, the certain weight loss and high decomposition tem-

perature demonstrated that P4VP was stable enough for directing

mesostructure in M-TiO2-ns under high temperature hydrother-

mal conditions, which was basically occluded in the mesopores of

M-TiO2-195 sample.

3.1.5. XPS measurements

Fig. 6 shows the XPS spectra of M-TiO2-195, M-TiO2-390 and

nonporous TiO2. Clearly, all the samples exhibited obviously sig-

nals of Ti2p and O1s (Fig. 6A), the high resolved signals of Ti at

around 458.6459.2, and 464465 eV were attributed to the sig-

nals of Ti2p3 and Ti2p1, indicating Ti4+ in these samples (Fig. 6B).

Inaddition, exceptforthe signals ofTi2pand O1s, newsignal associ-

ated with N1s could also be found in M-TiO2-390 and M-TiO2-195(Fig. 6A), which was resulted from the remove of P4VP template

during calcination. Moreover, the high resolved signals of N1s in

M-TiO2-390 and M-TiO2-195 exhibited broad peaks around 400eV

(Fig. 7c), which may be attributed to the formation of the TiON

bond. Correspondingly, the introduction of N in M-TiO2-ns could

also be proved by the peak shifting of Ti2p as compared with that

of nonporous TiO2 (Fig. 6B).

3.1.6. UV diffuse reflectance

Fig.7 showsthe UVvis diffuse reflectanceover various samples.

Clearly, all the samples exhibited excellent optical response to UV

light with different absorbance intensities. For example, M-TiO2-ns

and nonporous TiO2 exhibited strongest band-to-band absorption

with the band edge starting from 270 nm and ending up to 400 nmin the ultraviolet region, which could be assigned to the intrinsic

band gap absorption of anatase phase in the sample [42]. Interest-

ingly, compared with nonporous TiO2, M-TiO2-195 exhibited very

low adsorption intensities between 400500 nm in the visible light

region, which could be resulted from the introduction of N element

in the sample [43], in agreement with the XPS results.

3.2. Catalytic tests

3.2.1. Photo catalytic oxidation

Fig. 8 shows the kinetic curves in UV light induced oxidation of

RhB over various samples. Clearly, there were very little reduction

of concentrations of RhB after stirring of the mixture for 30min

under darkness, indicating very low content of RhB was adsorbed

468 466 464 462 460 458 456

Ti 2p1

B

c

bIntensit

y(a.u.)

Binding energy (eV)

Ti 2p3

a

800 750 700 650 600 550 500 450 400 350 300

A

c

b

a

O1s

Ti 2p

Intensity(a.u.)

Binding energy (eV)

N1s

410 408 406 404 402 400 398 396 394 392 390

C

c

b

N1s

Intensity(a.u.)

Binding energy (eV)

a

Fig. 6. XPSspectraof (A)survey,highresolved XPSof (B) Ti and (C)N (a)nonporous

TiO2, (b) M-TiO2 -390 and (c) M-TiO2-195.

by thesamples. Interestingly, when the mixture wasexposed to UV

light, M-TiO2-390 and M-TiO2-195 showed much higher catalytic

activities than those of nonporous TiO2 and M-TiO2-F127, which

was even comparable with that of commercial P25. For example,

only for 20min, the concentration of RhB catalyzed by M-TiO2-195

changed from 38.5 to 13.9ppm, similar with that of M-TiO2-390

(38.715.9 ppm), much lower than the solutions catalyzed by non-

porous TiO2 (39.330.5 ppm) and M-TiO2-F127 (39.520.7 ppm),

which were even as low as that of P25 (39.413.3ppm). Further

increasing the reaction time to 60min, the concentrations of RhB

catalyzed by M-TiO2-195 and M-TiO2-390 were decreased to only

0.12 and 1.52ppm respectively, which was as low as that of P25

7/27/2019 1-s2.0-S0169433212007015-main

6/7


300 400 500 600 700a

bAb

sorbance(a.u.)

Wavelength (nm)

c

Fig. 7. UVvis diffuse reflectance spectra of (a) nonporous titanium dioxide, (b)

M-TiO2-390 and (c) M-TiO2-195.

0 50 100 150 200 250

0

10

20

30

40

e

Darkness UV-Irradiation

Irradiation time (min)

C0

RhB(ppm)

d

c

ba

Fig. 8. Photo catalytic kinetic curves of oxidation degradation of RhB over (a) P25,

(b) M-TiO2-195, (c) M-TiO2-390, (d)M-TiO2-F127 and (e)nonporous TiO2.

(0.09ppm). In contrast, the concentration of RhB catalyzedby non-

porous TiO2 and M-TiO2-F127 were still up to 18.5 and 7.1ppm.

The above results demonstrated the excellent photocatalytic activ-

ities of M-TiO2-ns. The superior catalytic activities of M-TiO2-ns

were resulted form its novel characters of stable mesostructure,

crystalline mesopore walls, high BET surface areas and nitrogen

atom doped in the sample, the presence of nitrogen atom results in

the partial sorption in visible light region, which would be helpful

for improving their photocatalytic activities [43]. More impor-

tantly, even after recycled for three or five times, M-TiO2-195 still

showed very good catalytic activities as compared with that of

fresh M-TiO2-195 (Fig. 9B and C), suggesting its good recyclability.

which would be potentially importantfor their widely applications

[43].

It was also observed that P25 exhibited relative low surface

area as compared with M-TiO2-ns, which showed a little higher

catalytic than those of M-TiO2-ns. Consideration of lower surface

area of P25, the major difference between P25 and M-TiO2-ns was

their distinguished different crystal phase. Clearly, P25 was com-

posed of both anatase andrutile phases. Whereas the frameworkof

M-TiO2-ns was mainly composed of anatase phase, their different

compositions played a key role for theirdifferentcatalytic activities

[44].

3.2.2. Photo catalytic reduction

Except for photo catalytic oxidation reaction, M-TiO2-195 was

also activein UV light induced reductionof BDE209, a kind of bioac-

cumulative and toxic compound [4548], which had been widely

used as flame retardants in numerous consumer products in recent

years. However, there were still fewer reports on degradation of

BDE209 through photo catalytic reduction processes up to now.

Interestingly, M-TiO2-195 showed very good catalytic activities

for degradation of BDE209. For example, only after 25min, more

than 25% of BDE209 in the solution disappeared (Fig. 10a) when

catalyzed by M-TiO2-195. Moreover, after recycled for five times,

M-TiO2-195 still showed very good catalytic activities (Fig. 10a) for

degradation of BDE209, indicating its good recyclability. The above

results demonstrated that M-TiO2-ns could be used as efficient andrenewable photo catalysts in both photo oxidation and reduction

for degradation of organic pollutions, which would be potentially

importantfor theirwidely applications for environment protection

in our modern lives.

0 15 30 45 60 75 900

10

20

30

40

ADarkness

C0

RhB(ppm

)


Darkness UV-Irradiation

0 15 30 45 60 75 90

C


DarknessDarkness UV-Irradiation

0 15 30 45 60 75 90

B


DarknessDarkness UV-Irradiation

Fig. 9. Photo catalytickinetic curvesin oxidationof RhB over (A)fresh M-TiO2-195, (B) M-TiO2-195 afterbeingrecycled forthreetimesand (C) recycled M-TiO2-195 forfive

times.

7/27/2019 1-s2.0-S0169433212007015-main

7/7


0 5 10 15 20 250.70

0.75

0.80

0.85

0.90

0.95

1.00

b

C/C

0


a

Fig. 10. Photo catalytic reductionof BDE209 over the(a) M-TiO2-195 and (b) recy-

cled M-TiO2 -195 forfive times.

4. Conclusion

M-TiO2-ns has been successfully synthesized through novel

complex bond interaction between P4VP template and Ti precur-sor under high temperature hydrothermal conditions, the samples

show highly degree of crystallinity, large BET surface areas, uni-

form mesopores, and stable framework. Interestingly, M-TiO2-ns

showed good catalytic activities and recyclability in both UV light

induced oxidation and reduction as compared with those of M-

TiO2-F127 and nonporous TiO2, which are even comparable with

that of commercial P25. Combination of the advantages of good

crystallization, uniform and stable mesopores, and excellent photo

catalytic activities and recyclability, M-TiO2-ns will open new

routes for synthesis of stable and efficient photo catalysts for envi-

ronmental protection.

Acknowledgments

This work wassupported bythe Foundation of Shaoxing Univer-

sity (20125005) and Innovation Group of Science and Technology

Agency of Zhejiang Province. We also thank for Dr. Suns helps for

the photo catalytic tests.

References

[1] U. Bach, D. Lupo, P. Comte, J.E. Moser, F. Weissrtel, J. Salbeck, H. Spreitzer, M.Grtzel, Nature 395 (1998) 583585.

[2] A. Hagfeldt, M. Grtzel, Accounts of Chemical Research 33 (2000) 269277.[3] M. Anpo, M. Takeuchi, Journal of Catalysis 216 (2003) 505515.[4] F.F. Gao, Y. Wang, D. Shi, J. Zhang, M.K. Wang, X.Y. Jing, R. Humphry-Baker, P.

Wang, S.M. Zakeeruddin, M. Grtzel, Journal of the American Chemical Society130 (2008) 1072010728.

[5] P.D. Yang, D.Y. Zhao, D.I. Margolese, B.F. Chmelka, G.D. Stucky, Nature 396

(1998) 152155.[6] H.X.Li, Z.F.Bian,J. Zhu,D.Q. Zhang,G.S. Li, Y.N.Huo, H.Li, Y.F.Lu,Journalof the

American Chemical Society 129 (2007) 84068407.[7] X.C. Wang,J.C. Yu,C. Ho,Y.D. Hou, X.Z. Fu, Langmuir 21 (2005)25522559.[8] A. Maldotti, A. Molinari, R. Amadelli, Chemical Reviews 102 (2002) 3811

3836.[9] G.J.D. Soler-illia, C. Sanchez,B. Lebeau,J. Patarin, Chemical Reviews 102 (2002)

40934138.

[10] H.Q. Wang, M. Miyauchi, Y. Ishikawa, A. Pyatenko, K. Koshizaki, Y. Li, L. Li, X.Y.Li, Y. Bando, D. Golberg, Journal of the American Chemical Society 133 (2011)1910219109.

[11] J. Tang, Y.Y. Wu, E.W. McFarland, G.D. Stucky, Chemical Communications 40(2004) 16701671.

[12] W.Y.Dong, Y.J. Sun, C.W. Lee, W.M. Hua, X.C. Lu, Y.F. Shi, S.C. Zhang,J.M. Chen,D.Y. Zhao, Journal of the American Chemical Society 129 (2007) 1389413904.

[13] M.A. Carreon, S.Y. Choi, M. Mamak, N. Chopra, G.A. Ozin, Journal of MaterialsChemistry 17 (2007) 8289.

[14] A. Fujishima, K. Honda, Nature 238 (1972) 3738.[15] Z. Zou, J. Ye, K. Sayama, Nature414 (2001) 625627.

[16] X. Chen,S.S. Mao, Chemical Reviews 107(2007) 28912959.[17] R.L. Liu, Y.J. Ren, Y.F. Shi, F. Zhang, L.J. Zhang, B. Tu, D.Y. Zhao, Chemistry of

Materials 20 (2008) 11401146.[18] X.X. Zou, G.D. Li, K.X. Wang,L. Li,J. Su,J.S. Chen, Chemical Communications 46

(2010) 21122114.[19] Z.Q. Sun, J.H. Kim, Y. Zhao, F. Bijarbooneh, V. Malgras, Y. Lee, Y.-M. Kang, S.X.

Dou, Journal of the American Chemical Society 133 (2011) 1931419317.[20] P. Prene, E. Lancelle-Beltran, C. Boscher, P. Belleville, P. Buvat, C. Sanchez,

Advanced Materials 18 (2006) 25792582.[21] T. Hua,S.X.Ouyang, Y.P.Bi,N. Umezawa, M. Oshikiri,J.H.Ye, AdvancedMaterials

24 (2012) 229.[22] K.L. Frindell,M.H. Bartl,A. Popitsch,G.D. Stucky, Angewandte ChemieInterna-

tional Edition 41 (2002) 960962.[23] D. Grosso, G.J.A.A. Soler-Illia, F. Babonneau, C. Sanchez,P.-A. Albouy, A. Brunet-

Bruneau, A.R. Balkenende, Advanced Materials 13 (2001) 10851090.[24] S.Y. Choi, B. Lee, D.B. Carew, M. Mamak, F.C.Peiris,S. Speakman, N. Chopra,G.A.

Ozin, Advanced Functional Materials 16 (2006) 17311738.[25] P.D. Yang, D.Y. Zhao, D.I. Margolese, B.F. Chmelka, G.D. Stucky, Chemistry of

Materials 11 (1999) 28132826.

[26] F. Schth, Chemistry of Materials 13 (2001)31843195.[27] B. Ohtani, Y. Ogawa, S.J. Nishimoto, Journal of Physical Chemistry B 101(1997)

37463752.[28] J. Lee, M.C. Orilall,S.C. Warren, M. Kamperman, F.J. Disalvo, U. Wiesner, Nature

Materials 7 (2008) 222228.[29] J.C. Yu, X. Wang, X. Fu, Chemistry of Materials 16 (2004)15231530.[30] B.L. Kirsch, E.K. Richman, A.E. Riley, S.H. Tolbert, Journal of Physical Chemistry

B 108 (2004) 1269812706.[31] X.J. Meng, T. Kimura, T. Ohji, K. Kato, Journal of Materials Chemistry19 (2009)

18941900.[32] H.S. Yun, K. Miyazawa, H.S. Zhou,I. Honma,M. Kuwabara, Advanced Materials

13 (2001) 13771380.[33] M. Ueda, R. Matsunaga, M. Ikeda, M. Ogawa, Material Transactions 49 (2008)

17061709.[34] G.S. Li,L.P. Li,J. Boerio-Goates, B.F.Woodfield,Journalof theAmerican Chemical

Society 127 (2005) 86598666.[35] F.J. Liu, C.J. Li, L.M. Ren, X.J. Meng, H. Zhang, F.-S. Xiao, Journal of Materials

Chemistry 19 (2009) 79217928.

[36] Y.Han, D.F.Li,L. Zhao, J.W.Song,X.Y. Yang, N.Li,Y. Di, C.J.Li,S. Wu, X.Z. Xu,X.J.Meng, K.F. Lin, F.S. Xiao, Angewandte Chemie International Edition 42 (2003)36333637.

[37] F. Bonino, A. Damin, S. Bordiga, C. Lamberti, A. Zecchina, Langumir 19 (2003)21552161.

[38] A.Hagfeldt, M. Grtzel, Chemical Reviews 95 (1995) 4968.[39] B. Smarsly, D. Grosso, T. Brezesinski, N. Pinna, C. Boissiere, M. Antonietti, C.

Sanchez, Chemistry of Materials 16 (2004) 29482952.[40] D.Y. Zhao,Q.S.Huo,J.L.Feng, B.F. Chmelka,G.D.Stucky,Journalof theAmerican

Chemical Society 120 (1998) 60246036.[41] J.W. Song, L.M. Ren, C.Y. Yin, Y.Y. Ji,Z.F.Wu,J.X. Li, F.-S. Xiao, Journal of Physical

Chemistry C 112 (2008) 86098613.[42] X. Yang, Y.H. Wang, L.L. Xu, X.D. Yu, Y.H. Guo, Journal of Physical Chemistry C

112 (2008) 1148111489.[43] R. Asahi, T. Morikawa, T. Ohwaki,K. Aoki, Y. Taga, Science 293(2001) 269271.[44] H. Zhang,X.J.Lv, Y.M.Li, Y.Wang, J.H. Li, ACS Nano4 (2010) 380.[45] M.J. Laguardia, R.C. Hale, E. Harvey, Environmental Science andTechnology 40

(2006) 62476254.[46] A. Li,C. Tai, Z.S. Zhao,Y.W.Wang, Q.H. Zhang,G.B.Jiang, J.T. Hu,Environmental

Science and Technology 41 (2007) 68416846.[47] ATSDR, Toxicological Profile for Polybrominated Biphenyls and Polybromi-

nated DiphenylEthers(PBBsandPBDEs), U.S.Department ofHealthand HumanServices,The Agency forToxic Substances andDisease Registry(ATSDR),Wash-ington, DC, 2004, http://www.atsdr.cdc.gov/toxprofiles/tp68.html (accessedon December, 2006).

[48] C.Y. Sun, D. Zhao, C.C. Chen, W.H. Ma, J.C. Zhao, Environmental Science andTechnology 43 (2009) 157162.
http://www.atsdr.cdc.gov/toxprofiles/tp68.htmlhttp://www.atsdr.cdc.gov/toxprofiles/tp68.html

1-s2.0-s0169433212007015-main

Documents