Influence of Suspension Plasma Spraying Process Parameters on TiO2 Coatings Microstructure
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Rutile
Photodegradation
Photoelectrochemistry
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Titanium Dioxide
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Various kinds of TiO2 photocatalysts have been practically applied in various fields. Knowing the exact surface properties is a prerequisite to develop further and efficient applications. However, the cause of the essential difference in the activities of the two polymorphs of TiO2, rutile and anatase, has not been clearly elucidated yet. We tried to clarify the cause in terms of active oxygen species (˙OH, ˙O2(-), and H2O2) photogenerated on the surfaces, which are considered practically involved in the photocatalytic reactions. It was revealed that for anatase the rate of ˙OH generation was high, but it decreased in the presence of H2O2. On the other hand, for rutile, ˙OH generation was very low but it increased in the presence of H2O2. The formation rate of ˙O2(-) for rutile was higher than that for anatase, suggesting that the photoinduced reduction process should not be accountable for the higher photocatalytic activity of anatase. Since the Ti-Ti distance on a rutile surface is smaller than that for anatase, rutile is capable of forming a surface structure such as Ti-OO-Ti, leading to readily form O2. The mechanism of fast coupling of two photoinduced conduction band holes to form Ti-OO-Ti was proposed, which is accountable for the lower reactivity of rutile. This mechanism was verified by the analysis of surface species with ATR-IR spectroscopy.
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Anodic oxidation of Ti has been used to produce layers of TiO2 consisting of anatase or rutile or a mixture of both. While the anatase phase of TiO2 is formed at lower anodization potentials, the formation of the rutile phase starts at potentials above 100 V due to electrical breakdowns. Defects with broad optical absorption in the infrared range are generated only in anodic TiO2 layers with coexisting anatase and rutile phases under ultraviolet illumination in water containing atmosphere. These defects partially disappeared by annealing at about 400 °C for 30 min. The reversible defect reaction takes place in the surface regions between the anatase and rutile phases. (© 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)
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The nanophase anatase of different size (the average is 40 nm) was synthesized with chemical precipitation method. Transition from nanophase and microphase anatase to rutile were investigated with Raman spectrum. The result indicated that rutile characteristic peak (446 cm-1) appeared after 1 h heat preservation at 900 degrees C for microphase anatase, raising the temperature characteristic peak intensity of rutile (446,610 and 231 cm-1) continued to increase and characteristic peak of anatase (639,515 and 397 cm-1) decreased bit by bit. After 1 h heat preservation at 1,100 degrees C anatase transformed into rutile. While the nanophase anatase transited into rutile entirely after 1 h heat preservation at 900 degrees C, which is about 200 degrees C lower than microphase anatase to rutile transition temperature.
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DTA and isothermal kinetic studies were carried out on the reactions of BaSO4 or BaCO3 with TiO2 (anatase and rutile) to BaTiO3. In the initial steps, the reactions of BaSO4 with TiO2 (anatase) proceeded to BaTi4O9, of BaSO4 with TiO2 (rutile) to BaTi3O7, and of BaCO3 with TiO2 (anatase and rutile) to Ba2TiO4, respectively. These reactions were connected with the formation of binary metal oxide through some intermediates, which are BaSO4 or BaCO3 incorporated with TiO2. The reactivity of anatase was higher than that of rutile in all reaction systems.
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Dye degradation study using anatase and rutile titania suggests maximum efficiency of about 88% using anatase phase for MB under short UV light however, the maximum degradation under long UV light was not more than 65% (anatase/ rutile/EBT).
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Degradation
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