Powder Technology 205 (2011) 289291

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Powder Technology
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Molten salt synthesis of SrTiO3 nanocrystals using nanocrystalline TiO2 as a precursor

Tian Xi Wang a, Shuang Zhi Liu b, Jun Chen a,
a b

School of Chemistry and Chemical Engineering, Henan Institute of Science and Technology, Xinxiang 453003, China College of Chemical Engineering, Kaifeng University, Kaifeng 475004, China

a r t i c l e

i n f o

a b s t r a c t
A molten salt method was proposed to synthesize SrTiO3 nanocrystals in the eutectic NaClKCl at 700 C for 6 h, by using the homemade TiO2 nanocrystals and commercial Sr(NO3)2 powder as raw materials. Besides, a control experiment with the commercial TiO2 submicron-sized crystallites as a precursor was also conducted. The structure and composition of the obtained products were characterized by powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The results from XRD and XPS revealed the preparation of pure cubic phase SrTiO3 powders. The TEM observation demonstrated that the nanocrystalline TiO2 precursor played an important role in the current molten salt synthesis of SrTiO3 nanocrystals, which were likely formed by the template formation mechanism. 2010 Elsevier B.V. All rights reserved.

Article history: Received 19 December 2009 Received in revised form 2 July 2010 Accepted 30 August 2010 Available online 7 September 2010 Keywords: Ceramics Semiconductors Nanocrystals Molten salt synthesis

1. Introduction SrTiO3 is an important ceramic material having wide uses in the catalysis, semiconducting, gas-sensing, nonlinear optical limiting, electroceramic industry, etc., [18]. It is widely accepted that the properties and practical performances of SrTiO3 are strongly related to its morphology, size, crystal defects, surface properties, etc., [18], which ultimately depend on the preparation methods and preparation conditions. Generally speaking, phase-pure, composition-homogeneous and size-uniform SrTiO3 nanocrystals can meet the basic requirements for the most of their intended purposes. Molten salt synthesis is one of the simplest methods for preparing complex oxides, in which the molten salt is used mostly as a reaction medium or aid [712]. It not only enables to lower the formation temperature and shorten the reaction time, but also can control the particle morphology and stabilize different polymorphs of the resultant products [712]. However, to our knowledge, the information about the molten synthesis of nanocrystalline SrTiO3 is rather limited by far. Herein, we report the scalable synthesis of pure cubic phase SrTiO3 nanocrystals by heating the homemade TiO2 nanocrystals and commercial Sr(NO3)2 powder in the eutectic NaClKCl salts (whose melting point is around 650 C [8]) at 700 C, which is much lower than the reaction temperatures (11001200 C) used in the conventional solid phase reaction processes [2,3]. Besides, a control experiment with the commercial TiO2 submicron-sized crystallites as a precursor is also conducted for comparison.

2. Material and methods All the chemical reagents used are analytically pure. Anatase phase TiO2 nanocrystals with the size of about 710 nm (whose TEM image is shown in Fig. 1(a)) were prepared by us through solvothermal treatment of tetra-n-butyl titanate (Ti(OC4H9)4) in a mixed solvent of waterethanol (Volwater:Volethanol = 1:3) at 180 C for 12 h. Submicron-sized TiO2 crystallites with the size of about 60230 nm (whose TEM image is shown in Fig. 1(b)) were purchased directly from the Shanghai Academe of Fine Chemicals. In the synthesis of SrTiO3, 3.0 mmol of the homemade TiO2 nanocrystals (or the commercial submicron-sized TiO2 crystallites), 3.6 mmol Sr(NO3)2 and 1.0 g of equimolar NaCl and KCl powders were mixed and ground homogenously in a carnelian mortar, then transferred to a corundum crucible. The crucible was heated in a Mufe furnace at 700 C for 6 h, then allowed to cool to an ambient temperature naturally. The residue solid was washed with 1 mol/l HNO3 aqueous solution and distilled water to remove the impurities, dried in air at 120 C, and nally white SrTiO3 powder was obtained. Powder XRD patterns were recorded on a German Bruker AXS D8 ADVANCE X-ray diffractometer. XPS measurements were conducted on a Thermo ESCALAB 250 XPS system with Al K radiation as the exciting source, where the binding energies were calibrated by referencing the C 1s peak (284.6 eV) to reduce the sample charge effect. TEM images were taken on a Holland Philips Tecnai-12 transmission electron microscopy. 3. Results and discussion

Corresponding author. Tel.: + 86 0373 3043529. E-mail address: chenjun0988@163.com (J. Chen). 0032-5910/$ see front matter 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.powtec.2010.08.068

Fig. 2 shows the XRD patterns of the products obtained using the homemade TiO2 nanocrystals (Fig. 2(a)) or the commercial TiO2

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T.X. Wang et al. / Powder Technology 205 (2011) 289291

Fig. 3. XPS survey spectrum of the product synthesized using the homemade TiO2 nanocrystals as a precursor.

The compositional purity of the as-synthesized SrTiO3 powders was further conrmed by XPS analysis. The XPS survey spectrum of the product obtained using the homemade TiO2 nanocrystals as a precursor is shown in Fig. 3, which disclosed the presence of only Sr, Ti and O components in this sample (the atomic ratio of Sr:Ti:O was also nearly 1:1:3, as in the stoichiometric SrTiO3), free from contamination

Fig. 1. TEM images of (a) the homemade TiO2 nanocrystals and (b) the commercial TiO2 submicron-sized crystallites.

submicron-sized crystallites (Fig. 2(b)) as a precursor. All the XRD peaks in Fig. 2(a) and (b) can be indexed to cubic perovskite structure SrTiO3 (JCPDS card no. 73-661), and no characteristic XRD peaks coming from the possible impurities such as Sr2TiO4, TiO2, Sr(NO3)2 and SrCO3, etc., were visible, indicating the preparation of phase-pure SrTiO3 powders by the current molten salt method.

Fig. 2. XRD patterns of the products synthesized using (a) the homemade TiO2 nanocrystals or (b) the commercial TiO2 submicron-sized crystallites as a precursor.

Fig. 4. TEM images of the products synthesized using (a) the homemade TiO2 nanocrystals or (b) the commercial TiO2 submicron-sized crystallites as a precursor.

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by Na, K and Cl. Moreover, no intermediate compounds containing Na, K and Cl were observed when the molten salt synthesis was conducted at 700 C for 06 h, suggesting that the molten NaClKCl eutectic salts acted as a mere solvent in the formation process of SrTiO3. Fig. 4 shows the TEM images of the SrTiO3 powders obtained using the homemade TiO2 nanocrystals (Fig. 4(a)) or the commercial TiO2 submicron-sized crystallites (Fig. 4(b)) as a precursor. It can be seen from Fig. 4(a) and (b) that the kinds of TiO2 used played an important role in the sizes of the as-synthesized SrTiO3 powders. While the product synthesized using the homemade TiO2 nanocrystals as a precursor comprised mostly cubic-shaped nanocrystals with the size of about 1143 nm, that synthesized using the commercial TiO2 submicron-sized crystallites as a precursor comprised mainly submicron-sized crystallites with the size of about 64182 nm. So far, two generally accepted mechanisms have been proposed to describe the process of molten salt synthesis according to solubility of the reactants in molten salts [812]. One is the template formation mechanism (or interfacial reaction controlled mechanism), and the other is the dissolutionprecipitation mechanism (or diffusion controlled mechanism). The product obtained in the former will retain the similar size and morphology of the insoluble or less soluble raw reactant; whereas in the latter, the size and morphology of the product will be different from the raw reactants [812]. Because the sizes and morphologies of the as-synthesized SrTiO3 nanocrystals (Fig. 4(a)) and submicron-sized crystallites (Fig. 4(b)) were more similar to their respective TiO2 precursors (Fig. 1(a) and (b)), the template formation mechanism may play a predominant role in the current molten salt synthesis of SrTiO3. 4. Conclusions Pure cubic phase SrTiO3 nanocrystals and submicron-sized crystallites were synthesized by heating the homemade TiO2 nanocrystals or

the commercial TiO2 submicron-sized crystallites and commercial Sr (NO3)2 powder in the eutectic NaClKCl salts at 700 C for 6 h. The sizes of the as-synthesized SrTiO3 depended on the kinds of TiO2 precursors, indicating that the formation process of SrTiO3 in the molten salts was mainly controlled by the template formation mechanism.

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