Materials Letters 63 (2009) 17611763

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Materials Letters
j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / m a t l e t

Fabrication and photocatalytic activity of TiO2 nanober membrane

Xiwen Zhang a,b,,1, Shiyou Xu b,1, Gaorong Han a
a b

State Key Laboratory of Silicon Materials Science, Department of Materials Science and Engineering, Zhejiang University, Hangzhou 310027, China Mechanical Engineering Department, Stevens Institute of Technology, Hoboken, New Jersey 07030, USA

a r t i c l e

i n f o

a b s t r a c t
Titanium dioxide is one of the best semiconductor photocatalysts available for photocatalysis. In this paper, titanium dioxide nanober membranes are prepared by post-anneal-assisted electrospinning process. The obtained membrane is composed of anatase titanium dioxide continuous and porous nanobers with diameters ranging from 65 to 115 nm. An optimized annealing scheme is determined. Photocatalytic measurements show that the photocatalytic efciency of the anatase TiO2 nanober membrane is 72%, which is highly superior to that of the anatase TiO2 thin lm (44%). It is believed that the large specic surface area intensively enhances the photocatalytic reactions and the good shape retention might be favorable for recuperability and practicality. The potential applications for environmental purication are discussed. 2009 Elsevier B.V. All rights reserved.

Article history: Received 4 November 2008 Accepted 9 May 2009 Available online 22 May 2009 Keywords: Fiber technology Electrospinning Nanomaterials Nanobers Photocatalytic activity

1. Introduction Titanium dioxide (TiO2) has been generally considered to be one of the best semiconductor photocatalysts available for photocatalysis [1], due to its high photoactivity, photodurability, chemical and biological inertness, mechanical robustness and low cost. Since photocatalytic reactions mainly take place on the surface of the catalyst, a high surface-to-volume ratio is of great signicance for increasing the decomposition rate. TiO2 nanoparticles and nanocrystalline thin lms have already shown very high photocatalytic activity [2,3]. Although a lot of progress has been achieved in these forms of TiO2, the poor recuperability and reutilization limitation for nanopowders and low contact area for thin lms are still challenges for their commercial applications. Nanobers are expected to solve these problems because they combine the advantages of nanopowders and thin lm: nanobers are continuous and easy to fabricate into mesoporous nanober membranes; they also consist of nanocrystals [4]. However, to our knowledge, previous investigations have been mainly focused on the electrospinning preparation processes for TiO2 nanobers [5,6], whereas very little empirical study was related to the photocatalytic property of TiO2 nanobers with diameter lower than 100 nm although some work have been done for 250 nm TiO2 bers [16]. There are various methods for the fabrication of TiO2 nanopowders [7,8], nanotubes [9] and nanowires [10], but there are only a few

methods used to produce TiO2 nanobers, such as electrospinning [5], hydrothermal [11], etc al. Among them, electrospinning is a mature method to produce continuous bers with diameters ranging from tens to hundreds of nanometers [12], making it easy to obtain mesoporous nanober membranes for water purication. In this paper, TiO2 nanober membrane was prepared by electrospinning with a post-annealing process. The fabrication parameters, including the post-annealing scheme were optimized systematically. TiO2 nanobers with pure anatase crystallization and diameters of 50 200 nm were obtained. Photocatalytic properties of TiO2 material in the form of electrospun nanober membranes and CVD-prepared lms were compared. The as-prepared nanostructures exhibited excellent catalytic activity in the photoreduction reaction of Rhodamine B. Their photocatalytic reaction mechanisms are discussed. Potential photocatalytic applications of the TiO2 nanober membranes are also proposed. 2. Experimental studies The electrospinning setup was described in ref. [4]. A solution containing 0.3 g of high-molecular-weight Poly (vinyl pyrrolidone) (PVP) (Aldrich, Mw ~ 1300000), 7 g of ethanol, 3 g of Ti (OC4H9)4 (Aldrich) was mixed with 6 g of ethanol using acetylacetone as a complexing agent. This mixing was followed by a magnetic stirring for ~ 2 h. The resulting precursor solution was immediately loaded into a plastic syringe equipped with stainless steel needle. A DC voltage of 15 kV was applied to the needle. The feeding rate was controlled by a syringe pump. A piece of ground-connected aluminum foil (2.5 g) was placed 5 cm below the tip of the needle to collect the nanobers. After electrospinning, the obtained ber mats were annealed in air between 350550 C for 13 h to obtain the anatase TiO2 nanober membrane.

Corresponding author. State Key Laboratory of Silicon Materials Science, Department of Materials Science and Engineering, Zhejiang University, Hangzhou 310027, China. E-mail address: zjuxu_sy@hotmail.com (X. Zhang). 1 These authors contributed equally to the work. 0167-577X/$ see front matter 2009 Elsevier B.V. All rights reserved. doi:10.1016/j.matlet.2009.05.038

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The thermo-gravimetric and differential thermal analyses (TGDTA) were performed on the as-spun ber mats to determine an optimized post-annealing schedule. A scanning electron microscope (SEM) was used to observe the morphologies of the nanobers. The X-ray diffraction (XRD) patterns were recorded using a Rigaku D/max 2550 diffractometer (Cu K radiation). The photocatalytic activity evaluation process is the same as described in ref. [13] The TiO2 nanober membranes with an area of 10.0 10.0 mm2 and weight of 20.0 mg were put into the Rhodamine B solution in a dark condition for 15 min to reach equilibrium for adsorptiondesorption. Then, the samples were irradiated by ultraviolet light for 2 h. The bers that dispersed in the solution were removed by centrifugation before UV measurements. Finally, a few milliliters of solution were drawn from the reaction mixture and loaded in a UVvis spectrophotometer (UV-1601, Rigaku, Japan). The relative concentration of Rhodamine B was monitored by comparing its characteristic absorption intensity of the 550 nm peak with that of the original Rhodamine B solution. The comparison of the TiO2 sample prepared by atmospheric pressure CVD (APCVD) method [14] with the same perpendicular projected area as that of TiO2 nanober membrane (10.0 10.0 mm2) and the same lm weight of ~20.0 mg, was also performed using the same photocatalytic measuring conditions. 3. Results and discussion Fig. 1 shows the thermo-gravimetric and differential thermal analyses (TGDTA) of a PVP/Ti (OC4H9)4. There are three thermogravimetric steps. The rst is between 71.2110 C, about 15% weight loss, which is due to the volatilization of adsorbed water and organic matter from the surface. The second is between 300.5318.3 C, with 36.9% weight loss, accompanied by a strong thermopositive peak (332.1 C) in the DTA curve. It is probably due to the decomposition of PVP lateral chains and other organic matters, and the crystallization from amorphous TiO2 to anatase TiO2. The third is around 435.3 C, with 30.4% weight loss, accompanied by a strong thermopositive peak (496.9 C) in the DTA curve, corresponding to the further decomposition of PVP fundamental chains and a further crystallization of TiO2 from anatase to rutile. As the temperature is higher than 435.3 C, there is no weight loss, indicating the completion of ignition loss from the organic constituent. According to the TGDTA results, the post-annealing scheme should be performed as (90 C 0.5 h + 310 C 1.5 h + 430 C 1.5 h), with a heatingup speed rate of 150 C/h. A typical SEM image of TiO2 nanober membrane is shown in Fig. 2. These bers form uniform and continuous layer over a large area, the green ber membrane can be as large as 5 cm in diameter (shown in Fig. 1), and the largest annealed membrane can be 4 cm2 without

Fig. 2. SEM images of TiO2 nanober membrane (a) annealed membrane with inserted EDS pattern (top) and an individual TiO2 nanober(bottom).

fracture. From the EDS pattern shown in Fig. 2 (top), only titanium and oxygen elements are detected, indicating the removal of C and H impurities from the brous membrane sample through the annealing processes. The inserted SEM image in Fig. 2 (bottom) shows an individually annealed TiO2 nanober with a diameter of 65 nm. The average diameter of about 100 nanobers was computed to be 90 25 nm using the high-magnication SEM images. The average diameter of the PVP/Ti (OC4H9)4 green bers is about 150 30 nm. This dimensional reduction could be explained by the loss of PVP and other organics from the green nanobers as well as the crystallization of TiO2 during the annealing process, as seen from the TGGTA curve. This larger magnication SEM image also shows that TiO2 nanober has a porous structure, which we attribute to the photocatalytic properties. Fig. 3 shows the XRD patterns of the nanober membrane samples before and after annealing. It is obvious that the original ber membrane is in an amorphous phase. After the annealing process, all peaks that belong to the anatase TiO2 show up. Thus a pure anatase poly-crystalline TiO2 matter with a preferred (101) orientation is conrmed. Using a calibration height of 550 nm for Rhodamine B characteristic peak from UVvis spectra, photocatalytic activities of the anatase TiO2 nanober membrane and the APCVD prepared TiO2 lm were compared. In order to provide a quantitative comparison, we used an APCVD prepared TiO2 lm sample as a guide sample, which held a

Fig. 1. TGDTA curve of PVP/Ti(OC4H9)4(Insertion:green electrospun bers).

Fig. 3. XRD patterns of the TiO2 nanober membrane before and after anneal.

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point of view, a TiO2 matter in the form of nanober membrane intertextured by a large quantity of TiO2 nanobers with diameters of 50200 nm also suggests good shape retention, which could be favorable for recuperability and practicality, especially in the applied elds concerning environmental purication of polluted water and air, etc. 4. Conclusions TiO2 nanober membranes were fabricated by electrospinning followed with post-annealing. An optimized post-annealing scheme was determined as: 90 C 0.5 h + 310 C 1.5 h + 430 C 1.5 h. Uniform and continuous large area TiO2 nanobers were obtained even with high temperature annealing process. Pure anatase poly-crystalline TiO2 with a preferred orientation of (101) is conrmed. Through comparison using a height of 550 nm for Rhodamine B characteristic UVvis peaks, the photocatalytic activity of brous membrane is 72%, which is much superior to that of the APCVD lm (44%). The large specic surface area and the good shape retention of TiO2 nanober membrane suggest potential applications of photocatalysis in elds involving environmental purication for polluted water and air, etc. Acknowledgements The authors would thank the nancial support from the Chinese National Natural Science Foundation (No. 50772098). References
[1] Fujishima A, Honda K. Nature 1972;238:37. [2] Xu Zhonghou, Jing Chuanyong, Li Fasheng, Meng Xiaoguang. Environ Technol Technol 2008;42(7):2349. [3] Asahi R, Morikawa T, Ohwaki T, Aoki K, Taga Y. Science 2001;293:269. [4] Xu Shiyou, Shi Yong, Kim Sang-Gook. Nanotechnology 2006;17:4497. [5] Li D, Xia Y. Nano Lett 2003;3:555. [6] Alves AK, Berutti FA, Clemens FJ, Graule T, Bergmann CP. Mater Res Bull 2009;44:312. [7] Roso Martina, Sundarrajan Subramanian, Pliszka Damian, Ramakrishna Seeram, Modesti Michele. Nanotechnology 2008;19:285707. [8] Akurati KK, Vital A, Fortunato G, Hany R, Nueesch F, Graule TJ. Solid State Sci 2007;247:9. [9] Robert Armstrong A, Armstrong Graham, Canales Jesfs, Bruce Peter G. Angew Chem Int Ed 2004;43:2286. [10] Boercker JE, Enache-Pommer E, Aydil ES. Nanotechnology 2008;19:095604. [11] Zhang Fei-Bao, Li Hu-Lin. Mater Sci Eng C 2007;27:80. [12] Li D, Xia Y. Adv Mater 2004;16:1151. [13] Heiko U, Bunz F. Adv Mater 2006;18:973. [14] Guo Y, Zhang X, Weng W, Han G. Thin Solid Films 2007;515:7117. [15] Gibson P, Schreuder-Gibson H, Rivin D. Colloids Surf A 2001;187:469. [16] Doh SJ, Kim C, Lee SG, Lee SJ, Kim H. J Hazard Mater 2008;154:118.

Fig. 4. Comparison of the height of 550 nm Rhodamine B characteristic peak from UV vis spectra, for samples of: (a) pure Rhodamine B solution; (b) APCVD prepared TiO2 lm; (c) anatase TiO2 nanober membrane.

surface area of 10.0 10.0 mm2 and a lm weight of 20.0 mg. TiO2 nanober membrane with the same perpendicular projected area (10.0 10.0 mm2) and the same weight (20.0 mg) was also prepared. Thus, under the irradiation of ultraviolet light for 2 h in the same conditions, photocatalytic activities of the above two samples could be evaluated quantitatively. From Fig. 4, it is obvious that the photocatalysis of the anatase TiO2 nanober membrane shows enhanced photocatalytic activity compared to that of the APCVD prepared sample. The calculated efciency is 44% for APCVD prepared TiO2 lm and 72% for electrospun TiO2 nanober membrane. Since the electrospun nanobers have approximately 12 orders of magnitude more surface area than found in thin lms [15], and the nanober itself has a porous structure, the surface absorption of Rhodamine B in the TiO2 nanober membrane is much more enhanced compared to the TiO2 lm. Under the irradiation of ultraviolet light, the electron-hole pair is generated and is easier to move to the surface of the bers due to a shorter migration length. Then the electrons reduce oxygen to water and the photogenerated holes will probably involve the initial oxidation of surface OH-groups to hydroxyl radicals which then oxidize the Rhodamine B absorbed on the nanober surface. It is conrmed that the photocatalytic ability of the TiO2 nanober membrane we obtained is much more enhanced compared to that of APCVD prepared TiO2 lm due to the high specic surface area and photocatalytic activity. Furthermore, from a photocatalytic application