J Sol-Gel Sci Technol (2013) 65:443451 DOI 10.

1007/s10971-012-2956-7

ORIGINAL PAPER

Preparation of nanocrystalline titanium dioxide bers using solgel method and centrifugal spinning
Heyi Liu Yan Chen Shiguang Pei Guishuang Liu Jinqiang Liu

Received: 12 October 2012 / Accepted: 28 December 2012 / Published online: 10 January 2013 Springer Science+Business Media New York 2013

Abstract This paper reports the study of the preparation and structural characterization of nanocrystalline titanium dioxide (TiO2) bers, which were prepared using solgel method with titanium tetrachloride (TiCl4) as the titanium source and acetylacetone as chelating agent to synthesize the poly-acetylacetonatotitanium (PAT) spinning solution, followed by centrifugal spinning and steam atmosphere heat-treatment. The molecule structure of the PAT was analyzed. Using the fourier transform infrared and 1H nuclear magnetic resonance spectrum. The microstructure of the TiO2 bers was observed by using scanning electron microscope, which showed that the bers diameters are in the range of 515 lm. The effects of the SiO2 doping were investigated by using high-resolution transmission electron microscope and X-ray diffractometer, and the conclusion is that SiO2 doping can efciently inhibit the grain growth of TiO2 bers and defer the phase transformation of anataseto-rutile. In fact, the grain size is 33.2 nm for the un-doped TiO2 bers heat-treated at 700 C, while the grain size is only 7.6 nm for the TiO2 bers doped with 15 wt% SiO2, which shows the possibility to obtain nano-crystalline anatase TiO2 bers at higher heat-treatment temperature. Keywords Solgel Titanium dioxide bers Silica doping Centrifugal spinning Characterization

1 Introduction In recent decades, the application of photocatalytic oxidation technology especially titanium dioxide (TiO2), has attracted particular attention to help solve many serious environmental pollution problems [13]. With the advantages of chemical stability, low cost, non-toxic and high catalytic activity, TiO2 is studied mostly in the photocatalysis eld. Based on the UV radiation, TiO2 can generate highly oxidative free radicals, which can inevitably decompose various organic compounds into water and carbon dioxide [4]. There are many factors that affect the application of TiO2, such as the morphology, crystal structure, grain size, surface area and porosity. The large-scale application of TiO2 photocatalysis of traditional TiO2 nano-powders are prevented by their shortcomings of easy to reunion, difcult to recovery and reuse. To solve the problems above, various new morphologies such as TiO2 bers [59], nanobers [1012], nanorods [13, 14], nanotubes [15, 16], and hollow spheres [17, 18] have been prepared and studied. The preparation and utilization of TiO2 bers have become one of the hottest research elds. Especially, the solgel method is widely used to obtain TiO2 bers with high performance [5, 7, 19, 20]. Besides, two-step method [10, 21, 22], solvothermal reaction [23], and iron-exchange reaction [24] were also used to prepare brous TiO2 materials. Currently, there are several spinning technologies to prepare the precursor bers, such as dry-spinning [5, 7], wet-spinning [25], melting spinning [26] and electrostatic spinning [8, 19, 30]. Centrifugal spinning is one of the dry-spinning technologies, and it is an efcient and simple method for the preparation of brous materials. In addition, it has been proved that TiO2/ SiO2 nanocomposites have better photocatalytic activities than pure TiO2 [2729].

H. Liu (&) Y. Chen S. Pei G. Liu J. Liu School of Materials Science and Engineering, Nanjing University of Science and Technology, Nanjing 210094, Peoples Republic of China e-mail: liuheyi@mail.njust.edu.cn

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TiCl4 + 3H2 O + CH3 COCH2 COCH3 CH3 OH + 4N(C2 H5 3 4C2 H5 3 N HCl + PAT

Fig. 2 Optical image of the spinning solution Fig. 1 Flow diagram for preparation of TiO2 bers

In this paper, TiO2 bers doped with silica (SiO2) were prepared by using solgel method to synthesize the spinning solution,followed by centrifugal spinning and steam atmosphere heat-treatment. The precursors structure, crystal phase, grain size and morphologies of TiO2 bers were characterized.

2 Experiments 2.1 Synthesis of SiO2-doped TiO2 bers The synthesis process of TiO2 bers is shown in Fig. 1. To synthesis poly-acetylacetonatotitanium (PAT) spinning solution, titanium tetrachloride (TiCl4), acetylacetone (Acac), triethylamine (TEA) and deionized water (H2O) were used as raw materials, and absolute methanol (CH3OH) and tetrahydrofuran (THF) were used as solvent. 200 mL CH3OH was dropwise added into 40 mL TiCl4 with stirring at 025 C (in ice-water bath) in fuming cupboard. 20 mL H2O, 37.3 mL Acac and 202.1 mL TEA were diluted with 100, 112 and 202 mL CH3OH respectively. Then according to the order above, three kinds of solution were dropwise added into TiCl4/CH3OH solution with vigorous stirring at 025 C. The reaction solution would be stirred at room temperature for 0.5 h to synthesize PAT according to the reaction equation supposed as follows:
Fig. 3 Schematic diagram of the centrifugal spinning device

Fig. 4 Optical image of the obtained TiO2 bers

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room temperature, at last nanocrystalline TiO2 bers were obtained (optical image is shown in Fig. 4). 2.2 Characterization The fourier transformation infrared (FT-IR) spectrum of the PAT precursor was recorded in the range of 4,000400 cm-1, on a FT-IR spectrometer (Nicolet Magna-750, Nicolet, America) by using KBr pellets, where the PAT precursor were grounded into ne powders, diluted with KBr powders, and then pressed into a pellet. The 1H nuclear magnetic resonance (1H-NMR) spectrum of the PAT precursor was tested on an Ultra shielded superconducting Fourier transform NMR spectrometer (Advance600, Bruker, Switzerland) by using DMSO as solvent. The scanning electron microscope (SEM) and energy dispersive spectroscopy (EDS) of TiO2 bers were obtained by using a scanning electron microscope (S-2500, Hitachi, Japan). High-resolution transmission electron microscope (HR-TEM) images and the selected area electron diffraction (SAED) patterns of TiO2 bers were taken on a JEOL JEM-2100 (Japan). The phase transformation of TiO2 bers heat-treated to different temperatures was recorded by using an X-ray diffractometer (XRD, D8-Advance, Bruker, Germany), with Cu Ka1 radiation. Intensities of the diffraction peaks were recorded in the range of 2080 with a step size of 0.05. The BET specic surface area and pore structures of TiO2 bers were measured by N2 adsorptiondesorption method using a gas sorption analyzer (Omnisorp-100CX, Coulter, America). Before being tested, the bers were ground slightly, and degassed for 12 h at 350 C under 105 Pa. 3 Results and discussion 3.1 The structure of the PAT precursor To study the structure of the PAT precursor, the FT-IR spectrum and 1H-NMR spectrum were investigated as shown in Figs. 5, 6, respectively.

Fig. 5 FT-IR spectrum of the PAT precursor

After reaction completed, a golden solution was obtained and then concentrated to dry. 400800 mL THF was added into the dry residue, followed with vacuum ltration to remove the triethylamine hydrochloride (TEAHCl) precipitation which is insoluble in THF. Then the ltered solution was concentrated to dry to obtain the PAT precursor. 100 mL CH3OH was added into the dry PAT precursor to dissolve with stirring, and amount of (030 wt% SiO2 doping content) tetraethyl orthosilicate (TEOS) diluted in about 150 mL CH3OH was added into the PAT/CH3OH solution as an additive to TiO2. The solution mixture was concentrated to obtain spinning solution with a suitable viscosity of about 50 Pas (optical image is shown in Fig. 2). By using a self-made centrifugal spinning device (as shown in Fig. 3), with rotating speed of 18,00022,000 r/min, spinning disk with diameter of 4 cm and spinning hole with diameter of 0.3 mm, the spinning solution was shot out under the centrifugal force from the spinning holes distributed on the disc. The continuous PAT xerogel precursor bers were formed and solidied while the spout out spinning solution went through the 80120 C drying hot air around the spinning disk. Put the as-prepared precursor bers into a programming furnace to make it heat-treated under steam atmosphere from room temperature to 400900 C with a heating rate of 1.5 C/min, after that, made them all held at elevated temperature for 2 h and cooled to
Fig. 6 a 1H-NMR spectrum of the PAT precursor; b 1H-NMR spectrum of the possible impurity mixture

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446 Fig. 7 Attributions of chemical shift peaks in 1H-NMR spectrum

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3.1.2 1H-NMR spectrum Figure 6a shows that the 1H-NMR spectrum of the PAT precursor contain a number of chemical shifts peaks. In order to ascertain the attribution of each peak accurately, we prepared a possible impurity mixture containing TEAHCl, CH3OH, THF, and Acac, which existed in PAT synthesis reaction process and possibly remained a little in the PAT precursor, and then measured its 1H-NMR spectrum as shown in Fig. 6b. By excluding the chemical shift peaks of the possible impurity mixture in Fig. 6b, the remaining peaks in Fig. 6a can be easily assigned. The detailed attributions of all chemical shift peaks in 1 H-NMR spectrum in Fig. 6a are shown in Fig. 7. It can be seen that the components of the PAT precursor are very complicated. Not only poly-acetylacetonatotitanium, but also di-acetylacetonatotitanium, acetylacetonatotitanium monomer, as well as the impurity substances of TEAHCl, CH3OH, THF, and Acac (enol and keto form) are contained in the PAT precursor. According to the analysis of FT-IR and 1H-NMR, the probable chain structure of PAT is thus suggested as shown in Fig. 8. With -OH as joint group and Acac as side group, double chain molecular structure of PAT with a relatively large degree of polymerization may be formed, which makes the PAT sol spinning solution a good spinnability. 3.2 Characterization of TiO2 bers 3.2.1 SEM images and EDS spectrum The SEM micrographs of the as-prepared TiO2 bers heattreated at 700 C with 15 wt% SiO2 doping are shown in Fig. 9. It can be seen that the bers are smooth and

Fig. 8 The probable chain structure of the PAT molecule

3.1.1 FT-IR spectrum In Fig. 5, the main absorption peaks attributions are as follows: 3,371 cm-1 (m-OH), 1,619 cm-1 (d-OH), and 400600 cm-1 (mTiO). And the absorption peaks of Acac are all reected, such as the stretching vibration of C=O bond at 1,624, 1,475, and 776 cm-1, while the stretching vibrations of CC bond at 1,534 cm-1. The remaining peaks from 2,700 to 650 cm-1 can be attributed to 2,695 cm-1 (mCH), 1,423 cm-1 (dCH), 1,356 cm-1 (dSCH3 OH ), 1,289 cm-1 (dCH mCCH3 ), 1,030 cm-1 (pCH3 ), 870 cm-1 (mCCH3 ) and 658 cm-1 (pCCH3 ? ring distortion). In addition, the existence of the large and wide OH stretching vibration at 3,371 cm-1 and the TiO stretching vibration in the range of 400600 cm-1 indicate TiOH groups contained in the PAT precursor. It is remarkable that the broad absorption peak (wave number of 3,371 cm-1) is attributed to the associated -OH group, but not the dissociated -OH group, indicating that the -OH group in the PAT precursor joins with two Ti and forms to chain molecule.

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J Sol-Gel Sci Technol (2013) 65:443451 Fig. 9 a, b SEM images of the obtained TiO2 bers (700 C, with 15 wt% SiO2 doping); c EDS spectrum of spot 1 in b; d EDS spectrum of spot 2 in Fig. 9b

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uniform, whose diameters are in the range of 515 lm. The elemental composition of the bers is determined by EDS analysis and presented in Fig. 9c, d, which show that the bers are composed of TiO2 and SiO2, whose relative content is about 85 and 15 wt%, respectively. 3.2.2 HR-TEM images and SAED patterns The HR-TEM images and selected area electron diffraction patterns of the obtained TiO2 bers are presented in Fig. 10. It can be seen from Fig. 10 that the two kinds of TiO2 bers (without SiO2 doping and with 15 wt% SiO2 doping, respectively) are both consisted of nano-sized anatase TiO2 grains, which arranged disorderedly to form a polycrystalline microstructures. However, the grain sizes of the two bers are very different, although the heat-treatment temperature and holding time of the two bers are the same (400 C/2 h). The un-doped samples grain size is about

10 nm, and the doped samples is about 5 nm. The results indicate that the SiO2 doping can inhibit the grain growth of the TiO2 grains, which is very consistent with the results of XRD. 3.2.3 XRD analysis Figure 11 shows the XRD patterns of TiO2 bers heattreated at different temperatures under steam atmosphere. It can be observed from Fig. 11a, b that, whether doped or not, there are signicant anatase diffraction peaks at 400 C. With the heat-treatment temperature increasing, the diffraction peaks of anatase increase gradually and become sharp, which indicates the grain growth of TiO2 bers. When the heat-treatment temperature rising to 700 C, obvious rutile peaks appear in the un-doped TiO2 bers, and anatase completely transforms into rutile at 900 C (as shown in Fig. 11a). However, only anatase exists in the sample doped with 15 wt% SiO2 even up to 1,000 C (as shown in Fig. 11b).

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Fig. 10 a, b HR-TEM images of TiO2 bers (400 C, with no SiO2 doping); c SAED patterns of TiO2 bers (400 C, with no SiO2 doping); d, e HR-TEM images of TiO2 bers (400 C, with 15 wt% SiO2 doping); f SAED patterns of TiO2 bers (400 C, with 15 wt% SiO2 doping)

According to the equation f A

100 % I 1:26IR
A

[31], where

f(A) is the percentage content of anatase in the sample, IA and IR are the intensities of (101) peak of anatase and

(110) peak of rutile respectively, the ratios of rutile in the un-doped sample at 700 and 800 C are 30.6 and 66.2 %, respectively. Based on the Scherrers equation (Dhkl = 0.89k/b cosh), it can be calculated that the grain sizes of

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J Sol-Gel Sci Technol (2013) 65:443451 Fig. 11 XRD patterns of TiO2 bers heat-treated at different temperatures: a with no SiO2 doping; b with 15 wt% SiO2 doping

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Fig. 12 a XRD patterns and b grain size graph of TiO2 bers doped with different contents of SiO2 heat-treated at 700 C

un-doped bers grow rapidly from 10.8 nm (400 C) to 64.5 nm (900 C). But the grain growth of 15 wt% iO2 doped bers slows down signicantly, the grain sizes increase only from 5.2 nm (400 C) to 8.2 nm (900 C). Figure 12 represents the XRD patterns and grain size graph of TiO2 bers doped with different contents of SiO2 and heat-treated to 700 C. Figure 12a reveals that there is no rutile phase appearing in the samples except the un-doped one. Figure 12b shows that the grain size decreases with increasing of SiO2 doping content, and at last the grain size is approximately to be a constant (about 7 nm). According to the Scherrers equation, the grain size of un-doped bers is 33.2 nm (700 C), but the grain size of the doped bers is only 9.7 nm (5 wt% SiO2), 7.6 nm (15 wt% SiO2), and 7.2 nm (30 wt% SiO2), respectively.

The results of XRD imply that appropriate addition of SiO2 can inhibit the grain growth and delay the phase transformation of anatase-to-rutile. It can surmise that the addition of SiO2 hinders the mutual contact of TiO2 to prevent the grain growth and the nucleation of rutile [20]. 3.2.4 BET specic surface area and pore structure The adsorptiondesorption isothermal curves for TiO2 bers doped with 15 wt% SiO2 heated to 700 C are shown in Fig. 13. The isotherm is a representative IV type with larger hysteresis loop. The BET surface area of bers is 164.3 m2/g, which is very benecial to adsorb organic molecule in the water which needs to be puried. The pores are ink

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nano-crystalline anatase TiO2 bers at higher heat-treatment temperature.

Acknowledgments This work was supported by the Natural Science Foundation of Jiangsu Province under Grant No. BK2009390 and Nanjing University of Science Technology Research Funding (No. 2010GJPY087 and No. 2010ZDJH07).

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Fig. 13 Nitrogen adsorptiondesorption isotherm of the TiO2 bers (700 C, 15 wt% SiO2)

Fig. 14 Pores diameter distribution of the TiO2 bers (700 C, 15 wt% SiO2)

bottle type, and the result calculated by using the DFT method shows that the pore diameter is mainly concentrated around 4.5 nm, as shown in Fig. 14.

4 Conclusions In summary, nanocrystalline TiO2 bers were successfully prepared by solgel method and centrifugal spinning in this paper. The molecular structure of the PAT precursor was deduced to be double chain structure with -OH as joint groups and Acac as side groups. Moreover, the morphologies, phases, grain sizes, BET specic surface area and pore structure of TiO2 bers were studied. The results showed that the bers are smooth and uniform, with diameters in the range of 515 lm and grain size about 510 nm. At 700 C, the BET surface area of TiO2 bers with 15 wt% SiO2-doping is about 164.3 m2/g, and the pore diameter is mainly concentrated around 4.5 nm. Besides, it has been veried that SiO2 doping were investigated, and the conclusion is that SiO2 doping can efciently inhibit the grain growth of TiO2 bers and defer the phase transformation of anatase-to-rutile, so as to obtain

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