Characterization of Zr-Doped TiO 2 Nanocrystals Prepared by a Nonhydrolytic Sol−Gel Method at High Temperatures
Highly crystalline and surface-modified Zr-doped TiO(2) nanorods were successfully prepared using a nonhydrolytic sol-gel method that involves the condensation of metal halides with alkoxides in anhydrous trioctylphosphine oxide (TOPO) at either 320 or 400 degrees C. In addition, the interaction of the cross-condensation between the Ti and Zr species was studied by characterizing the morphologies, crystalline structures, chemical compositions, surface properties, and band gaps of the nanocrystals obtained at different reaction temperatures and Zr-to-Ti stoichiometric ratios. Increases in the concentration of Zr(4+) and in the reaction temperature led to large nanorods and regular shapes, respectively. In addition, only the anatase form was observed in the Zr-doped TiO(2) nanorods. The Zr-to-Ti ratios obtained ranged from 0.01 to 2.05, all of which were far below the stoichiometric ratios used during the preparation of the samples (0.25-4). Moreover, the Zr(4+) units accumulated mainly at the surface of the TiO(2) nanocrystals. The band gaps of the Zr-doped TiO(2) nanorods ranged from 2.8 to 3.8 eV, which are smaller than those of pure TiO(2) (3.7 eV) or ZrO(2) (5.2 eV). The Zr-doped anatase TiO(2) nanorods prepared at 400 degrees C at an initial stoichiometric Zr-to-Ti ratio of 2:3 exhibited the highest photoactivities for the decomposition of rhodamine B because of the presence of trace amounts of Zr(4+) (Zr/Ti = 0.03) in the TiO(2) and the regular shapes of these particles. DSC analysis indicated that the temperatures for forming nanocrystalline TiO(2) and ZrO(2) were 207 and 340 degrees C, respectively. Moreover, the reactivities of condensation between the Ti species were reduced when Zr species were involved in the NHSG reactions. The results obtained in this study clearly demonstrate that the faster kinetics for the generation of TiO(2) controls the material properties as well as the photoactivities of the nonhydrolytic sol-gel-derived nanocrystals.
Available from: Marek Dziadosz
- "In recent years, titania dioxide have attracted a great interest due to many real and potential applications. In these applications, titanium dioxide is used as a component of various types of composites of some significance in production of pharmaceuticals, cosmetics or paints [1, 2], drug delivery systems with controlled release [3–5], solar cell [6–9], chemical sensing [10–12], luminescent material, and photocatalyst for, e.g., water purification [13–16]. In the wide field of organic–inorganic composite materials, titanium dioxide is a popular filler of organic matrices. "
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ABSTRACT: Polymer (XAD7HP)/Ti(4+) nanocomposites were prepared through the swelling of polymer in titanium (IV) ethoxide as a titanium dioxide precursor. The nanocomposite beads exhibit relatively high porosity different than the porosity of the initial polymer. Thermal treatment of composite particles up to 200 °C in vacuum causes the change of their internal structure. At higher temperature, the components of composite become more tightly packed. Calcination at 600 °C and total removal of polymer produce spherically shaped TiO2 condensed phase as determined by XRD. Thermally treated composites show the substantial change of pore dimensions within micro- and mesopores. The presence of micropores and their transformation during thermal processing was studied successfully by positron annihilation lifetime spectroscopy (PALS). The results derived from PALS experiment were compared with those obtaining from low-temperature nitrogen adsorption data.
Available from: Yongchun Zhao
- "To make use of sunlight as energy source for photocatalysis and improve photocatalytic oxidation efficiency, many attempts have been devoted to develop TiO 2 -based photocatalysts with high photocatalytic performances. These attempts include surface modification  , metal or nonmetal ion doping  , generation of oxygen vacancies , combination with other semiconductors , etc. Among these methods, doping metal oxides into TiO 2 has attracted considerable interest since these junction systems could prevent the recombination of charge carriers and decrease the band gap. "
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ABSTRACT: Nanofibers prepared by an electrospinning method were used to remove elemental mercury (Hg(0)) from simulated coal combustion flue gas. The nanofibers composed of different metal oxides (MO(x)) including CuO, In(2)O(3), V(2)O(5), WO(3) and Ag(2)O supported on TiO(2) have been characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersing X-ray (EDX) and UV-vis spectra. The average diameters of these nanofibers were about 200nm. Compared to pure TiO(2), the UV-vis absorption intensity for MO(x)-TiO(2) increased significantly and the absorption bandwidth also expanded, especially for Ag(2)O-TiO(2) and V(2)O(5)-TiO(2). Hg(0) oxidation efficiencies over the MO(x)-TiO(2) nanofibers were tested under dark, visible light (vis) irradiation and UV irradiation, respectively. The results showed that WO(3) doped TiO(2) exhibited the highest Hg(0) removal efficiency of 100% under UV irradiation. Doping V(2)O(5) into TiO(2) enhanced Hg(0) removal efficiency greatly from 6% to 63% under visible light irradiation. Ag(2)O doped TiO(2) showed a steady Hg(0) removal efficiency of around 95% without any light due to the formation of silver amalgam. An extended experiment with 8 Hg(0) removal cycles showed that the MO(x)-TiO(2) nanofibers were stable for removing Hg(0) from flue gas. Factors responsible for the enhanced photocatalytic activities of the MO(x)-TiO(2) nanofibers were also discussed.
Available from: C.P. Chin-pao Huang
- "Addition of transition metal ions as dopants to prolong the recombination time or shift the adsorption wavelength to visible region is one of the promising methods to improve the degradation efficiency and rate of organic pollutants in aqueous solutions (Stylidi et al., 2004; Chatterjee and Dasgupta, 2005; Tayade et al., 2006; Zhou et al., 2007). Several transition or noble metal ions at different mass loadings have been used to improve the photodegradation efficiency of organic compounds by TiO 2 (Kapoor et al., 2005; Chang and Doong, 2006). However, the enhanced efficiency of metal-doped TiO 2 toward organic photodegradation is highly dependent on the metal ions used. "
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ABSTRACT: The photoassisted reduction of metal ions and organic dye by metal-deposited Degussa P25 TiO(2) nanoparticles was investigated. Copper and silver ions were selected as the target metal ions to modify the surface properties of TiO(2) and to enhance the photocatalytic activity of TiO(2) towards methylene blue (MB) degradation. X-ray powder diffraction (XRPD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM) were used to characterize the crystallinity, chemical species and morphology of metal-deposited TiO(2), respectively. Results showed that the particle size of metal-deposited TiO(2) was larger than that of Degussa P25 TiO(2). Based on XRPD patterns and XPS spectra, it was observed that the addition of formate promoted the photoreduction of metal ion by lowering its oxidation number, and subsequently enhancing the photodegradation efficiency and rate of MB. The pseudo-first-order rate constant (k(obs)) for MB photodegradation by Degussa P25 TiO(2) was 3.94 x 10(-2) min(-1) and increased by 1.4-1.7 times in k(obs) with metal-deposited TiO(2) for MB photodegradation compared to simple Degussa P25 TiO(2). The increase in mass loading of metal ions significantly enhanced the photodegradation efficiency of MB; the k(obs) for MB degradation increased from 3.94 x 10(-2) min(-1) in the absence of metal ion to 4.64-7.28 x 10(-2) min(-1) for Ag/TiO(2) and to 5.14-7.61 x 10(-2) min(-1) for Cu/TiO(2). In addition, the electrons generated from TiO(2) can effectively reduce metal ions and MB simultaneously under anoxic conditions. However, metal ions and organic dye would compete for electrons from the illuminated TiO(2).
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