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Catalysis Communications 10 (2009) 13541357

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Catalysis Communications
journal homepage: www.elsevier.com/locate/catcom

Photodegradation of organics over a new composite catalyst V2O5/SmVO4


Yiming He a,b, Tianlu Sheng a, Jianshan Chen a, Ruibiao Fu a, Shengming Hu a, Xintao Wu a,*
a b

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China College of Mathematics, Physics and Information Engineering, Zhejiang Normal University, Jinhua 321004, China

a r t i c l e

i n f o

a b s t r a c t
A visible light active photodegradation catalyst was prepared by coupling V2O5 with SmVO4. The best catalyst shows 99.5% conversion of acetone. It was also proved to be efcient for the photodegradation of methanol, 2-propanol, and benzene. The Pt doped VSmO composite catalyst has higher photocatalytic activity and complete oxidation ability. By BET, XRD, UVvis and PL techniques, the specic surface area, structure and optical properties of the catalyst samples were characterized. The high photodegradation activities of the VSmO and Pt/VSmO catalysts could be attributed to the enhanced charge separation by the electrons and/or holes transfer between V2O5 and SmVO4 semiconductors. Crown Copyright 2009 Published by Elsevier B.V. All rights reserved.

Article history: Received 19 December 2008 Received in revised form 20 February 2009 Accepted 27 February 2009 Available online 9 March 2009 Keywords: Photodegradation Photocatalyst V2O5 SmVO4

1. Introduction Since Fujishima and Honda reported photo-induced decomposition of water on TiO2 electrodes [1], a great deal of efforts have been devoted to the investigations of metal oxide semiconductor catalysts for environmental applications, such as air and water purication [2,3]. In terms of the high activity and chemical stability, TiO2 is an excellent photocatalyst that can mineralizes a large range of organic pollutants [4]. However, the band gap of TiO2 (anatase, 3.2 eV) limits its absorption to the ultraviolet region (<4%) of the solar spectrum. Hence, in order to make use of solar light source in photodegradation reaction, a visible light active photocatalyst is desired. Currently, most of the investigations in this area are focused on the improvements of metal ion or anion doped TiO2 catalysts [57]. But they usually can only use a very limited amount of visible light or show low activities in photodegradation of organic compounds. Coupling a large band gap semiconductor with a small band gap semiconductor is a possible way to synthesize the visible light driven photocatalyst. Since Serpone et al. [8] rst reported the coupled catalyst a large variety of coupled semiconductor systems have been reported, such as CdS/TiO2, WO3/TiO2, WS2/WO3, V2O5/MgF2 couples [816]. The semiconductor V2O5 has a small band gap of $2.0 eV. It should be active in a wide region of visible light wavelength (<600 nm), which cover most part of the solar light. So, V2O5 is a type of potential visible light active catalyst

and lots of photocatalysts containing V2O5 have been reported [1316]. In this paper, we present a new coupled catalyst containing V2O5 phase. SmVO4 is another phase in the coupled system. It was extensively used as an efcient catalyst for selective oxidation of light alkane [1719]. To the best of our knowledge, however, no studies have been focused on the photocatalytic performance of SmVO4. Herein, the V2O5SmVO4 catalyst was prepared and tested. The performance investigation indicates the VSmO composite catalysts show high photocatalytic activities on photodegradation of organic substrates under visible light. 2. Experimental 2.1. Catalysts preparation NH4VO3 (>99%), Sm(NO3)3 6H2O (>99%), and P25 (Degussa TiO2) as reference, were purchased commercially and used without further purication. V2O5 was obtained by calcination in air of NH4VO3 at 500 C for 4 h. SmVO4 was prepared by precipitation method: Solution of NH4VO3 and solution of Sm(NO3)3 with a V to Sm mole ratio of 1:1 were mixed to give a deposit. The PH value of the solution was adjusted to 78 by a solution of NH3H2O. After aged at room temperature for 5 h, the deposit was ltered, washed three times by water, dried at 100 C for 12 h and calcined at 500 C for 4 h. The VSmO composite catalysts were prepared by the following steps: Solution of NH4VO3 and Sm(NO3)3 were mixed and evaporated to give a solid precursor. After dried at 100 C for 12 h, the solid precursor was calcined at 500 C for 4 h and then cooled to room temperature to yield the catalyst. The VSmO

* Corresponding author. Tel.: +86 0591 83792294; fax: +86 0591 83714946. E-mail address: wxt@fjirsm.ac.cn (X. Wu).

1566-7367/$ - see front matter Crown Copyright 2009 Published by Elsevier B.V. All rights reserved. doi:10.1016/j.catcom.2009.02.021

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composite catalysts were denoted as VSm-1 (nV/nSm = 1), VSm-2 (nV/nSm = 1.5), VSm-3 (nV/nSm = 2.5), VSm-4 (nV/nSm = 3.5), and VSm-5 (nV/nSm = 4.5), respectively. The 0.1 wt%Pt/VSm-2 catalyst, denoted as Pt/VSm-2, was prepared by impregnationphotoreduction method: 4.5 g of VSm-2 catalyst was added into 3.0 mL of H2PtCl6 6H2O solution (Pt: 0.0015 g/mL). The sample was kept in the dark for 5 h, and then dried at 80 C for 10 h. After that, the dried sample was put on the Xe lamp irradiation for 2 h to obtain the 0.1 wt%Pt/VSm-2 catalyst. The 0.1 wt%Pt/SmVO4 catalyst (denoted as Pt/SmVO4) was prepared by the same method. 2.2. Catalytic tests The catalytic reaction under visible light was carried out in a glass tube (ID 5.0 mm) reactor which could cut off most of the UV light. Two 400 W xenon lamps were used as visible light sources. In each reaction, the bed length of catalyst (500 800 mg) is about 4.5 cm and the other part of the reactor was wrapped by aluminum paper to exclude the contribution of the blank reaction (Fig. 1). A thermocouple was put in the middle of the catalyst bed outside the reactor to detect the reaction temperature. The reactor tube was cooled by a fan. Because of the heat from the lamps, even we tried to cool down the reactor by the fan, the reaction temperature is still between 130 and 140 C. Pure oxygen was used as oxidant. The organic reactants (acetone, methanol, 2-propanol and benzene) were fed into the reactor by bubbling gas (O2) through liquid organic at 0 C (cooled in a water-ice bath) to obtain the reactant mixture. The ow of mixture was controlled at 8.0 mL/min. The concentration of organics was analyzed by GC and the organic/O2 molar ratio was shown in Table 1. The reaction products were analyzed on a GC (equipped with a GDX-203 column and a 5A carbon molecular sieve column) with TCD. All the data were collected after 3 h of online reaction. In order to rule out the thermal reaction, both the VSm-2 and Pt/VSm-2 catalysts were tested for acetone oxidation in dark at the same reaction temperature 140 C. The dark reaction shows that acetone did not react with oxygen over VSm-2 or Pt/VSm-2 catalysts at 140 C. The blank reaction was also tested. The result shows that no acetone was photodegradated without photocatalyst under visible light.

Table 1 Photodegradation of organics over VSm-2 and Pt/VSm-2 catalysts under visible light. Organics X Conversion (%) SCO2 (%) SCO (%) Sother (%) Acetone 0.10 99.5 (99.8) 43.3 (100) 56.6 (0) 0.1 (0)a Methanol 0.05 100 (100) 24.5 (100) 75.5 (0) 0 (0) 2-Propanol 0.01 99.1(100) 54.1 (100) 41.8 (0) 3.1 (0)b Benzene 0.022 48.0 (98.4) 77.9 (100) 22.1 (0) 0 (0)

Note: The numbers in bracket represent the performance of Pt/VSm-2 catalyst, X is the organic/O2 molar ratio. a Represents selectivity to acetol. b Represents selectivity to acetone.

2.3. Characterizations The XRD characterization of the catalysts was carried out on RIGAKU DMAX2500. The specic surface areas of the catalysts were measured on Autosorb-1 (Quantachrome Instruments). The UVvis spectra of the catalysts were recorded on Perkin Elmer Lambda900. The photoluminescence (PL) spectra of catalysts were collected on Horiba Jobin Yvon (FL3-P-TCSPC) instrument. The light source was a Xe lamp (excitation at 292 nm). 3. Results and discussion The XRD analysis (Fig. 2) shows that the VSmO composite catalysts with V/Sm mole ratio greater than 1 contain well-crystallized V2O5 (orthorhombic) and SmVO4 (tetragonal) phases. With the increase of V/Sm ratio from 1.5 to 4.5, the peak intensity of the V2O5 phase increases. There is no new peak observed in the XRD pattern of the VSmO composite catalyst, indicating that no new phase was generated. The XRD pattern of Pt/VSm-2 catalyst is also shown in Fig. 2. Obviously, such a small amount of Pt did not give rise to detectable changes in the XRD pattern. The UVvis spectra of Sm2O3, P25 (TiO2 Degussa), SmVO4, V2O5 and VSmO catalysts are shown in Fig. 3. The photoabsorption performance of the VSmO complex catalysts in the visible region is much stronger than that of Sm2O3 and P25. With the increase of vanadium content, the peak intensity in the visible region (400 600 nm) increases. But when the mole ratio of V to Sm is greater than 1.5, the UVvis spectra of the VSmO composite catalysts show a little difference. The P25, V2O5, SmVO4 and VSmO composite catalysts were tested in the photodegradation reaction of acetone under visible

Fig. 1. The reactor system.

Fig. 2. XRD patterns of catalysts.

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Fig. 3. UVvis spectra of catalysts.

light. The results are shown in Fig. 4. Under UV light, TiO2 has a high activity for acetone degradation [13]. But under visible light, TiO2 shows low activity like V2O5. Pure SmVO4 shows 64% conversion of acetone. However, its activity is still lower than the VSmO composite catalysts. As shown in Fig. 4, the acetone degradation conversion of the VSmO composite catalysts increases with the increase of V/Sm ratio from 1.0 to 1.5 and decreases at even higher V/

Fig. 4. Activities of catalysts on photodegradation of acetone under visible light, (a) the different catalysts, (b) life-testing of VSm-2 catalyst.

Sm ratio. The highest acetone conversion was obtained on catalyst VSm-2. The acetone conversion reached 99.5% and it was stable within 24 h of online reaction (Fig. 2b). The result of Fig. 4 shows that the VSmO composite catalysts are more active than both SmVO4 and V2O5. Obviously, doping of V2O5 to SmVO4 formulated a serious of active photodegradation catalysts. In the photodegradation of acetone, the typical degradation products are CO2, CO, acetol, and H2O. As an example, for the photodegradation of acetone over VSm-2, the selectivities to CO2, CO, and acetol are 43.3%, 56.6%, and 0.1%, respectively (Table 1). It means that the VSm-2 catalyst was not able to oxidize acetone completely. To promote the complete oxidation of organic pollutants over the catalyst, we doped the VSm-2 catalyst with a small amount of metal Pt. Only CO2 and H2O were detected in Pt/VSm-2 catalyst. The results indicate Pt/VSm-2 catalyst is a better photodegradation catalyst in terms of complete oxidation. The similar phenomenon also occurred over SmVO4 and 0.1 wt%Pt/SmVO4. The 0.1 wt%Pt/SmVO4 catalyst could oxidize acetone more completely than SmVO4 (not shown here). But the photoactivity (91.7% conversion of acetone) was lower than Pt/VSm-2. Obviously, both V2O5 and Pt were needed to obtain the best photocatalytic performance. The Pt doped VSm-2 catalyst was also proven to be efcient for the oxidation of methanol, 2-propanol, and benzene (Table 1). The specic surface area of catalyst might be a factor to inuence activity of the catalysts. So, all the catalysts were characterized by BET method. The VSmO composites have larger surface areas than V2O5 (6 m2/g) and SmVO4 (11 m2/g). The specic surface areas of VSm-1, VSm-2, VSm-3, VSm-4, VSm-5 and Pt/VSm-2 catalysts are 40, 35, 35, 28, 21, 34 m2/g, respectively. Obviously, the change in specic area is not in good agreed with that in activity. The specic area is not a major factor to inuence the catalytic activity. The most important factor to inuence the activity is the composition of the catalysts. The characterizations have revealed that only the V2O5 and SmVO4 phases exist in the VSmO composite catalysts. V2O5 is inactive because of the rapid recombination of electron-hole pairs [13]. But when it was coupled with SmVO4 the photocatalytic activity was greatly improved. It shows the typical phenomenon of the coupled photocatalyst. So, it is plausible that the stronger photoactivity of the VSmO composite catalysts results from the coupling effect between V2O5 and SmVO4. That means the photogenerated electrons or holes transfer between V2O5 and SmVO4 semiconductors might occur. This simultaneous charge transfer could increase the space charge separation, limit their recombination and thus promote the photo-oxidation efciency [12]. In order to prove the above suggestion, the band energy potential of the V2O5 and SmVO4 semiconductors is needed. However, it is difcult to determine the band edge position of semiconductor and we are doing this work. Herein, we support another proof. The photoluminescence spectra of the photocatalysts are useful to disclose the migration, transfer, and recombination processes of the photogenerated electron-hole pairs in the semiconductor. Fig. 5 shows the PL emission spectra of SmVO4 and VSm-2 catalyst. The PL spectrum of SmVO4 shows two strong emissions at 563 and 600 nm, which indicate the electrons and holes recombine rapidly [20,21]. However, over VSm-2 catalyst, the peaks intensity is greatly decreased. It suggested that the doped V2O5 decreased the electron-hole pair recombination. Of course, V2O5 also could be the centers of recombination reaction. There was an optimum dosage for the V2O5 phase. When the vanadium concentration was higher than its optimal level (VSm-2 catalyst), V2O5 would promote the recombination reaction and decreased the photocatalytic activity. The addition of metal (such as Pt, Ag, Pd, etc.) to photocatalyst is another way to control electron-hole pairs recombination [13,22,23]. In this paper, a little amount of Pt was doped into

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catalyst design was also proved to be valid in catalysts with other compositions such as V2O5/GdVO4 and V2O5/EuVO4, which will be published elsewhere. Acknowledgements This work was supported by grants from the 973 Program (2007CB815301 and 2006CB932904), the National Science Foundation of China (20333070, 20673118 and 20871114), the Science Foundation of CAS (KJCX2-YW-M05) and of Fujian Province (2006L2005, 2007F3118). References
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catalyst VSm-2 and the activity was greatly promoted. This is because the doped Pt retards the recombination of photon electronhole pairs by forming the Schottky barriers at each Pt-semiconductor contacting region [23]. 4. Conclusion In conclusion, the visible light active VSmO composite catalyst was prepared and the VSm-2 catalyst (nV/nSm = 1.5) was found to be the best one. When Pt was doped into VSm-2 catalyst the catalytic activity was improved and the complete oxidation of organic substrates was enhanced. The high photodegradation activities of the VSmO and Pt/VSmO catalysts could be attributed to the enhanced charge separation by the electrons and/or holes transfer between V2O5 and SmVO4 semiconductors. The idea of the photo-