Applied Surface Science 258 (2012) 74487454

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Applied Surface Science

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

High-temperature hydrothermal synthesis of crystalline 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

a b s t r a c t
Mesoporous titanium dioxide with crystalline mesopore walls (M-TiO2 -ns) have been successfully synthesized through the self-assembly of poly 4-Vinylpyridine template and tetrabutyl titanate precursor based on their complex bond interaction under high temperature (180 C) hydrothermal conditions. X-ray diffraction shows that M-TiO2 -ns have highly crystalline mesopore walls with anatase phase characters; N2 sorptiondesorption isotherms, SEM and TEM images show that M-TiO2 -ns have high BET surface areas (85 and 120 m2 /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 35 m. Interestingly, M-TiO2 -ns exhibit much higher catalytic activities and good recyclability in both induced reduction of decabromodiphenyl and oxidation of Rhodamine B under UV light than those of nonporous crystalline TiO2 and M-TiO2 templated by hydrocarbon surfactant of F127, which is even comparable with that of commercial P25. Combination of the unique characters such as crystallinity, stable mesostructure, large BET surface areas and superior photo catalytic activities make M-TiO2 -ns a kind of potentially important material for removing of organic pollutions in environment through green photo irradiation processes. 2012 Elsevier B.V. All rights reserved.

Article history: Received 6 March 2012 Received in revised form 5 April 2012 Accepted 9 April 2012 Available online 21 April 2012 Keywords: High temperature synthesis Crystalline mesoporous TiO2 Complex bond interaction Photo catalysis Recyclability

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 activities, superior chemical stabilities, low cost and environmental friendly [121], which results in their potentially important applications in the elds of photoconductors, sensors, biology active materials, dye sensitized solar cells and photocatalysts [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 (EOn POm EOn ) as structure directing agents [2226], the synthetic temperature is usually kept below 140 C due to relative lower thermal stabilities of the surfactant templates. However, the low synthetic temperature usually results in the samples with amorphous frameworks. Nevertheless, for efcient 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 elds of solar cells or photo catalysis.

Corresponding authors. Tel.: +86 575 88345681; fax: +86 575 88345681. E-mail address: qichenze@usx.edu.cn (C.-Z. Qi). 0169-4332/$ see front matter 2012 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.apsusc.2012.04.059

Generally, the transformation of amorphous TiO2 to crystalline form such as anatase or rutile usually demands of high temperature (400 C) 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 lower temperature (160 C) [33,34]. Very recently, Xiao et al. have successfully synthesized a series of ordered and stable mesoporous materials under high temperature (up to 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 (180 C) hydrothermal route, 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 temperature (550 C), the mesostructure of M-TiO2 -ns was intact, and the accompanied enhanced crystalinity also happened. In contrast, MTiO2 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 7 m2 /g, respectively) and poor porosities. More importantly, M-TiO2 -ns exhibited

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much higher catalytic activities and good recyclability in both UV light induced reduction degradation of decabromodiphenyl ether (BDE209) and oxidation degradation of organic dye of Rhodamine B (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 (PEO106 PPO70 PEO106 , 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 reuxing. As a typical run, 2.0 g of 4-Vinylpyridine monomer was dissolved into a solution containing 10 mL of ethanol and 0.05 g of AIBN initiator, then the mixture was rapidly heated to 80 C, after vigorous stirring for 6 h, the P4VP template with molecular weight about 26,000 was obtained. 2.2.2. Synthesis of M-TiO2 -ns M-TiO2 -ns (where n stand for the molar ratio of titanate/P4VP) were synthesized by self assembly of tetrabutyl titanate with P4VP template at room temperature, hydrothermally treatment at 180 C for 24 h, and calcination was done at 550 C for 5 h. As a typical run for synthesis of M-TiO2 -195, 2.0 g of P4VP template was dissolved into 50 mL of ethanol, then 15 mmol of tetrabutyl titanate was added into the mixture under vigorous stirring, obviously precipitate was formed. After the ethanol slowly evaporates at room temperature under stirring, a brown solid was obtained almost after 48 h. The obtained solid was transferred into an autoclave and was subjected to hydrothermal treatment at 180 C for 48 h. Calcination 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 designated as M-TiO2 -F127, which could be obtained from self assembly of titanium isopropoxide with F127 under acid condition. As a typical run, 2.0 g of F127 was dissolved into a mixture containing 76 mL of water and 3.3 mL of HCl (10 M), followed by addition of 40 mmol of titanium isopropoxide, after stirring at 40 C for 20 h, a gel was formed, which was immediately transferred into an autoclave for further condensation at 180 C for another 24 h, then the obtained product was collected by ltration, drying in air, and calcination at 550 C for 5 h. 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-ltered 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 diffuse reectance spectra were recorded on a Perkin-Elmer Lambda

A A A A/R A

A: anatase R: rutile A/R A f e d c b a

Intensity (a.u.)
10

20

30

40

50

60

70

80

2Theta (degree)
Fig. 1. Wide angle XRD patterns 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 images were performed on JSM-6700F electron microscopes. XPS spectra were performed on a Thermo ESCALAB 250 with Al K radiation, and binding energies were calibrated using the C1s peak at 284.9 eV. Thermogravimetric analysis (TG) was performed on a Perkin-Elmer TGA7 and a DTA-1700 in owing air. 2.4. Catalytic test 2.4.1. Photo reduction UV light induced photo catalytic reduction of BDE209 was carried out in a cylindrical glass under irradiation by a PLS-SXE300 300 W xenon lamp equipped with a 360 nm cutoff lter. As a typical run, 5.0 mg of catalyst was added into a cylindrical glass containing 5 mL of BDE209 solution with the concentration of 2 105 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 for 30 min and sonicated for 1 min under darkness, then the Pyrex vessel was purged with argon for 30 min for removing of oxygen. At a given time interval of irradiation, small aliquots were withdrawn and analyzed using Shimadzu HPLC system (LC-20AT pump and UV/vis SPD-20A detector). 2.4.2. Photo oxidation UV light induced photo catalytic oxidation of RhB was also carried out in a cylindrical glass under irradiation by a PLS-SXE300 300 W xenon lamp. As a typical run, 50.0 mg of catalyst was added into a cylindrical glass containing 50 mL of RhB solution with the concentration of 40 ppm. Before irradiation, the mixture was stirring under darkness for 30 min until the sorption was achieved equilibrium. At a given time interval of irradiation, small aliquots were withdrawn, ltered and analyzed by UV spectroscopy. 3. Results and discussion 3.1. Structural characterizations 3.1.1. XRD Fig. 1 shows the XRD patterns of various samples. For the as synthesized 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 conditions (Fig. 1b). In contrast, the mesoporous TiO2 synthesized at

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a b c
dV/dlogD (cm /g)

0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0

200

Volume adsorption (cm /g)

d
160

120

80

40

c d
0 20 40 60 80 100

0.0

0.2

0.4

0.6

0.8

1.0

-0.1

Relative pressure (p/p0 )

Pore diameter (nm)

Fig. 2. N2 isothermals and pore size distribution of (a) M-TiO2 -195, (b) M-TiO2 -390, (c) M-TiO2 -F127 and (d) nonporous TiO2 .

relative lower temperature (100 C) exhibited amorphous mesopore 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 the samples of M-TiO2 -F127 and M-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 under high temperature hydrothermal conditions. Notably, the crystalline mesopore walls would result in their good structural stability and good photo catalytic properties. 3.1.2. N2 sorption isotherms Fig. 2 shows the N2 sorptiondesorption isotherms and the correspondingly 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. SEM images of M-TiO2 -195.

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

the presence of obviously mesostructure in the samples (Fig. 2a and b), which gave high BET surface areas (85 and 120 m2 /g respectively, Table 1) and uniform pore diameter around 1214 nm (Fig. 2a and b, Table 1). Obviously, the BET surface areas of MTiO2 -ns were much higher than that of commercial P25 (45 m2 /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 (0.18 and 0.04 cm3 /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

(85 m2 /g, Table 1), indicating the higher content of P4VP template 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 35 m (Fig. 3a). High resolved SEM images showed that the sample exhibited porous surface with the pore size around 1015 nm, suggesting their abundant nanoporosity. Fig. 4 shows the TEM images of MTiO2 -ns, which exhibited wormhole like mesopores with pore size around 1214 nm, 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 welldened 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].

Table 1 The textural parameters of various samples. Run 1 2 3 4 5 Samples M-TiO2 M-TiO2 M-TiO2 -F127 Nonporous TiO2 P25 SBET (m2 /g) 120 85 31 7 45 Vp (cm3 /g) 0.34 0.32 0.18 0.04 0.17 Dp (nm) c 11.9 14.4 28.5

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1.0

A
0.9

O1s Ti 2p

0.7

Intensity (a.u.)

0.8

TG (%)

N1s c

0.6 0.5 0.4 0.3 0.2 100 200 300 400 500 600 700 800

b a
800 750 700 650 600 550 500 450 400 350 300

Temperature (C)
Fig. 5. TG curve of as synthesized M-TiO2 -195.

Binding energy (eV)

B

Ti 2p3 Ti 2p1

3.1.4. Thermal analysis Fig. 5 shows the TG curve of as synthesized M-TiO2 -195. Clearly, M-TiO2 -195 had a weight loss of 32% centered at 420 C, which was resulted from the decomposition of P4VP template in the sample. Apparently, the certain weight loss and high decomposition temperature demonstrated that P4VP was stable enough for directing mesostructure in M-TiO2 -ns under high temperature hydrothermal 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 signals of Ti2p and O1s (Fig. 6A), the high resolved signals of Ti at around 458.6459.2, and 464465 eV were attributed to the signals of Ti2p3 and Ti2p1, indicating Ti4+ in these samples (Fig. 6B). In addition, except for the signals of Ti2p and O1s, new signal associated 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 400 eV (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 reectance Fig. 7 shows the UVvis diffuse reectance over 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 nm in the ultraviolet region, which could be assigned to the intrinsic band gap absorption of anatase phase in the sample [42]. Interestingly, 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 30 min under darkness, indicating very low content of RhB was adsorbed

Intensity (a.u.)

a
468 466 464 462 460 458 456

Binding energy (eV)

C N1s

Intensity (a.u.)

b a

410

408

406

404

402

400

398

396

394

392

390

Binding energy (eV)

Fig. 6. XPS spectra of (A) survey, high resolved XPS of (B) Ti and (C) N (a) nonporous TiO2 , (b) M-TiO2 -390 and (c) M-TiO2 -195.

by the samples. Interestingly, when the mixture was exposed 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 20 min, the concentration of RhB catalyzed by M-TiO2 -195 changed from 38.5 to 13.9 ppm, similar with that of M-TiO2 -390 (38.715.9 ppm), much lower than the solutions catalyzed by nonporous TiO2 (39.330.5 ppm) and M-TiO2 -F127 (39.520.7 ppm), which were even as low as that of P25 (39.413.3 ppm). Further increasing the reaction time to 60 min, the concentrations of RhB catalyzed by M-TiO2 -195 and M-TiO2 -390 were decreased to only 0.12 and 1.52 ppm respectively, which was as low as that of P25

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a
300 400 500 600 700

Wavelength (nm)
Fig. 7. UVvis diffuse reectance spectra of (a) nonporous titanium dioxide, (b) M-TiO2 -390 and (c) M-TiO2 -195.

40

Darkness UV-Irradiation

(0.09 ppm). In contrast, the concentration of RhB catalyzed by nonporous TiO2 and M-TiO2 -F127 were still up to 18.5 and 7.1 ppm. The above results demonstrated the excellent photo catalytic activities 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 importantly, even after recycled for three or ve 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 important for 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 composed of both anatase and rutile phases. Whereas the framework of M-TiO2 -ns was mainly composed of anatase phase, their different compositions played a key role for their different catalytic activities [44]. 3.2.2. Photo catalytic reduction Except for photo catalytic oxidation reaction, M-TiO2 -195 was also active in UV light induced reduction of BDE209, a kind of bioaccumulative and toxic compound [4548], which had been widely used as ame 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 25 min, more than 25% of BDE209 in the solution disappeared (Fig. 10a) when catalyzed by M-TiO2 -195. Moreover, after recycled for ve 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 efcient and renewable photo catalysts in both photo oxidation and reduction for degradation of organic pollutions, which would be potentially important for their widely applications for environment protection in our modern lives.

Absorbance (a.u.)

C0RhB (ppm)

30

20

e d c b a

10

0 0 50 100 150 200 250

Irradiation time (min)

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 .

Darkness Darkness
40

UV-Irradiation

Darkness Darkness

UV-Irradiation

Darkness Darkness

UV-Irradiation

30

C0RhB (ppm)

20

10

0 0 15 30 45 60 75 90 0
15 30 45 60 75 90

15

30

45

60

75

90

Irradiation time (min)

Irradiation time (min)

Irradiation time (min)

Fig. 9. Photo catalytic kinetic curves in oxidation of RhB over (A) fresh M-TiO2 -195, (B) M-TiO2 -195 after being recycled for three times and (C) recycled M-TiO2 -195 for ve times.

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1.00 0.95 0.90

C/C0

0.85 0.80 0.75 0.70 0 5 10 15 20 25

b a

Irradiation time (min)

Fig. 10. Photo catalytic reduction of BDE209 over the (a) M-TiO2 -195 and (b) recycled M-TiO2 -195 for ve times.

4. Conclusion M-TiO2 -ns has been successfully synthesized through novel complex bond interaction between P4VP template and Ti precursor under high temperature hydrothermal conditions, the samples show highly degree of crystallinity, large BET surface areas, uniform 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 MTiO2 -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 efcient photo catalysts for environmental protection. Acknowledgments This work was supported by the Foundation of Shaoxing University (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
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