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Single phases of Inl-xNixTaO4 were synthesized by a solid-state reaction at 1,100 ¡æ, using pre-dried In2O3, Ta2O5 and NiO (99.99% purity) as starting materials. To increase the photocatalytic activity of the materials, we used impregnation with aqueous Ni(NO3)2 or RuC13 solution to load the oxide semiconductor surface with 1.0 wt% partly oxidized nickel or RuO2; these loaded materials act as electron traps and hydrogen evolution sites. The Ni-loaded photocatalysts were calcined at 350 ¡æ for 1 h in air and reduced in H2 atmosphere (200 torr) at 500 ¡æ for 2 h, then treated in O2 atmosphere (100 torr) at 200 ¡æ for 1 h. The reduction-oxidation treatment produced a double-layered structure of metallic Ni and NiO (denoted NiOy) on the surface of the photocatalyst; this double-layered structure suppresses the backward reaction of water splitting, which is activated by metallic nickel surfaces. The Ru-loaded photocatalysts were calcined at 500 ¡æ for 2 h in air. The water-splitting experiments were carried out with 0.5 g powdered photocatalyst suspended in 250 ml of pure water in a Pyrex glass cell. A 300-W Xe arc lamp was focused through a shutter window and a 420 nm long pass filter was placed on the surface of the cell. The gases evolved were determined by the thermal conductivity detector (TCD) gas chromatograph, which was connetted to the glass-made gas circulating line attached to the Pyrex glass cell. The results of the photocatalytic reaction and photophysical parameters are listed in Table 1. The non-doped catalyst, NiOy/InTaO4 is active, but the activity was significantly enhanced by Ni doping of InTaO4. As a typical example, Fig. 2 shows the evolution of H2 and O2 from pure water containing suspensions of NiOy/In0.9Ni0.1Ta0.4 and RuO2/In0.9Ni0.1TaO4 under visible light irradiation (¦Ë>420 nm). The rates of H2 and O2 evolution were about 16.6 and 8.3 ¦Ìmolh-1, respectively, and the quantum yield at 402 nm was estimated to be 0.66% by using an interference filter (¦Ë=402 nm; half-width, 15.3 nm). For RuO2/In0.9Ni0.1TaO4, the rates of H2 and O2 evolution were about 8.7 and 4.3 ¦Ìmolh-1,respectively. The gas formation rate of the NiOy loaded sample is about twice as large as that of the RuO2-loaded sample. The gas evolution stopped when the light was turned off, showing that the reaction is induced by the absorption of visible light and not by tribological processes, such as the so-called mechano-catalysis. |
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