Nov 9 2010
Hyun-Ju Kim, Sung Bin Bae and Dong- Sik Bae
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AZojomo (ISSN 1833-122X) Volume 6 November 2010
Topics CoveredAbstractKeywords IntroductionExperimentalResults and DiscussionsConclusionsAcknowledgmentsReferenceContact Details
Ru doped TiO2 nanoparticles were prepared under high temperature and mild pressure conditions(0.1 MPa) by mixture from metal chloride solution and TiO2 sol. Ru doped TiO2 particles were reaction at the temperature range of 170°C-210°C for 6 h. The microstructure and phase of the synthesized particles were studied by TEM and XRD. Thermal properties of the synthesized powder were studied by TG-DTA analysis. X-ray diffraction pattern shows that the synthesized particles were crystalline. The effects of synthesis parameters, such as the concentration of starting solution, reaction temperature are discussed.
Ru doped TiO2 nanoparticles, Anatase, Rutile, Sol-Gel Process, Hydrothermal Process
Titanium dioxide is an important material for a variety of applications such as catalytic devices, solar cells, and other optoelectronic devices [1–3]. Especially, TiO2 is used in wide range of environmental photocatalyst because of its unique properties: it is a semiconductor with band gap about 3.2 eV possessing strong oxidative ability and non-toxicity. Titania is a well known n-type inorganic metal oxide semiconductor that is transparent to visible light and has a high refractive index. Due to its unique optical property and chemical stability, titania may be used in the splitting of water  and in the photo-oxidation processes. Solar cells demonstrating rather high photovoltaic efficiencies are studied in the frame of structures containing transparent conductive oxide (TCO)/dye sensitized titania/electrolyte systems which include the dye-sensitized nanocrystalline TiO2 solar cell . However, there are some disadvantages of its use in photocatalytic applications, namely the light adsorption in UV light spectrum region only and the high electron (e–) – hole (h+) recombination rate. Many attempts to improve the performance of TiO2 as a photocatalyst under UV illumination, and to improve its light absorption and conversion capacity in visible range of the solar spectrum, have been described in the literature in recent years [7, 8]. In this context, a large number of metal ions, particularly transition metal ions such as ruthenium, iron, chromium and cobalt, have been used as TiO2 dopants [9-11]
The coordination environment of the dopants is affected not only by the nature of the dopant such as ionic radii and concentration but also by the synthesis method . In this work, Ru3+ were used as dopants for TiO2 based materials to improve their properties, namely to extend the light absorption into the visible light region, to reduce the recombination of the photogenerated e– and h+ and to increase the surface area. Ru doped TiO2 powder has been obtained by sol–gel and hydrothermal method by a mixture from metal nitrates solution and TiO2 sol. Hydrothermal processes have the potential for the direct preparation of crystalline ceramic powders and offer a low-temperature alternative to conventional powder synthesis techniques in the production of oxide powders . This process can produce fine, high-purity, stoichiometric particles of single and multi-component metal oxides. Furthermore, if process conditions such as solute concentration, reaction temperature, reaction time and the type of solvent are carefully controlled, the desired shape and size of the particles can be produced [14-15]. A uniform distribution of the particles is important for optimal control of grain size and microstructure to maintain high reliability. It has been demonstrated that such powders are composed of much softer agglomerates and sinter much better than those prepared by calcination decomposition of the same oxides . These powders could be sintered at low temperature without calcination and milling steps [17-18].
The object of this study was to prepare Ru doped TiO2 nanoparticles by a combination of sol-gel and hydrothermal methods.
Titanium(IV) isopropoxide (Ti[OCH(CH3)2]4, JUNSEI Chemicals, 98%), Ruthenium chloride (RuCl3 •3H2O, KOJIMA Chemicals, 99%) and hydrochloric acid (HCl, Daejung Chemicals 35%) were used for the hydrothermal preparation. First, TiO2 sol was prepared metal alkoxide hydrolysis and condensation. Titanium (IV) isopropoxide was used as a precursor. It was slowly added to the ethanol(99.9%) as a solvent , with distilled water added for hydrolysis reaction. Finally, a small amount of hydrochloric acid was slowly added to the solution with stirring. After condensation reaction and crystallization, transparent suspended TiO2 sol was obtained. Ru solution (0.16 mol) was prepared by dissolving of RuCl3 •3H2O in distilled water. The weight percentage of the Ru:TiO2 precursor mixtures was kept to 1:39 mL. The resulting suspension was placed in a 1000 mL stainless steel pressure vessel. The vessel was then heated to the 170-210°C range at a rate of 5°C/min for 6 h. The resulting powder was washed with distilled water until pH 7 and then dried at 80°C for 24 h. The phase identification of synthesized powders was recorded by x-ray diffractometer (Philips X’pert MPD 3040). The structure, size and morphology of the resulting composites were examined by transmission electron microscopy (FETEM, JEOL 2100CF). For TEM studies, samples were prepared by adding drops of freshly prepared cluster solution on a carbon film supported on a Cu grid. Thermal decomposition behavior of the synthesized powder was studied by TG-DTA analysis (TA5000/SDT 2960 DSC Q10).
Results and Discussions
Fig. 1 shows an X-ray diffraction pattern of the Ru doped TiO2 particles as a function of reaction temperature. From the X-ray analysis, synthesized particles reveals the coexistence of anatase (JCPDS number 84-1286) and rutile (JCPDS number 01-1292) phases in the reaction temperature from 170°C to 210°C for 6 h. The intensity of rutile phase on Ru doped TiO2 particles increased with increasing reaction temperature. The amount of rutile phase on the synthesized particles increased with decreasing Ru concentration in solution because the less a content of the transposition metal, the easier to phase transition in the same temperature condition. The TEM microstructure of the synthesized Ru doped TiO2 particles as a function of reaction temperature is shown in Fig. 2. The average size of the synthesized Ru doped TiO2 particles increased with reaction temperature increased from 170°C to 210°C. Microstructure of synthesized particles shows a small particles size about 10-60nm and size distribution was unclear and broad. The Fig. 3 shown the spectrum of Ru doped TiO2 nanoparticles by TEM–EDS analysis. The peak of titanium, Ru and oxygen shows on the spectrum. From the TG-DTA analysis (Fig. 4) of Ru doped TiO2 nanoparticles, the overall reduction in weight was about 4.2% up to ~700°C and water of crystallization was dehydration at 242°C. Also it shows that transition of phase from anatase to rutile at almost 561°C. Specific Surface Area of synthesized particles as a function of Ru concentration in TiO2 by combination of a sol-gel and a hydrothermal process. BET surface areas of synthesized particles by a hydrothermal process were found to be larger than that of pure TiO2 from synthesized by a sol-gel process (about 50 m2/g). The surface of synthesized particles increased with increasing Ru concentration in TiO2 sol.
Figure 1. X-ray diffraction patterns of the synthesized particles as a function of reaction temperature synthesized powders : anatase (A) and rutile (R). (JCPDS number 84-1286, 01-1292)
Figure 2. TEM micrographs of the synthesized particles as a function of reaction temperature synthesized powders by combination a sol-gel process and a hydrothermal process : (a) 170°C, 6 h (b) 190°C, 6 h (c) 210°C, 6 h
Figure 3. EDS (Energy Dispersive Spectroscopy) spectrum of the synthesized Ru doped TiO2 particles by combination a sol-gel process and a hydrothermal process.
Figure 4. TG-DTA analysis of the synthesized Ru doped TiO2 nanoparticles by combination a sol-gel process and a hydrothermal process.
Ru doped TiO2 particles have been synthesized by a combination of a sol-gel and hydrothermal process. Nanosized Ru doped TiO2 particles were obtained in the temperature range of 170°C-210°C for 6 h. Microstructure of synthesized particles shows a small particles size around 10-60nm and size distribution was unclear and broad. The average size of the synthesized particles increased when reaction temperature increased. The crystalline phase of the synthesized Ru doped TiO2 particles shows the coexistence of anatase and rutile reaction at the temperature range of 170°C to 210°C for 6 h.
This research was financially supported by the Korea Sanhak Foundation(2008).
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Hyun-Ju Kim, Dong- Sik Bae
School of Nano & Advanced Materials Engineering, Changwon National Univ.,
Gyeongnam, 641-773, South Korea
E-mail : [email protected]
Sung Bin Bae
Korea Science Academy, 899 Danggam 3-dong, Busanjin-gu, Busan, Korea
This paper was also published in print form in "Advances in Technology of Materials and Materials Processing", 12 (2010) 9-12.