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After evacuating the reaction system and re-running the experiment, almost identical gas production rates were achieved in the second as well as third runs. More than 7,200 p,mol gases evolved(H2, about 4,800 ¦Ìmol; and O2, about 2,400¦Ìmol) during the course of a 400-h experiment. The catalyst samples remained unchanged during the course of reaction, suggesting that thephotocatalytic activity is stable under visible Light irradiation. The turnover number-the ratio of total amount of gas evolved to catalyst (1,412 ¦Ìmol in our system)Ò»exceeded 5 after 400 h reaction time. The turnover number in terms of reacted electrons relative to the amount of Ni loaded on the surface of the sample and Ni doped in InTaO4 reached 39 at 400h reaction time,indicating that the reaction occurs catalytically. Wavelength dependence of the photocatalytic gas evolution on the photocatalyst was investigated using different cut-off filters. As a comparison, the Pt/TiO2 photocatalyst (P-25) was measured using the same method. Although photocatalytic activity was observed when using Inl-xNixTaO4 and a cut-off filter of ¦Ë>500 nm, it is much lower than that observed under ¦Ë>420 nm light irradiation.The rates of H2 and O2 evolution were 1.91 and 0.86 ¦Ìmolh-1 on In0.9Ni0.1TaO4 respectively, under ¦Ë>500 nm Light irradiation. The activity disappeared when the wavelength of light irradiation was larger than 550 nm. The results are in good agreement with the observation of diffuse reflectance spectra (see Fig. 3). By contrast, no photocatalytic activity was obtained on Pt/TiO2 under visible light irradiation (¦Ë>420 nm). X-ray diffraction analysis showed that there is no observable structural difference between the samples before and after reaction. Full-profile structure refinement of XRD data was performed using the Rietveld program REITf1N12, showing that all samples crystallize in the same wolframite structure, monoclinic with space group P2/a, and that the lattice parameters decrease along all three axes as the Ni content ¦Ö is increased, as long as ¦Ö<0.15. Figure 4 shows the change of V/Z with doping content, where V and Z are cell volume and the number of formulas per cell, respectively. The inset shows the c-axis parameter as a function of Ni content, to illustrate the lattice parameter changes induced by doping. There is a linear decrease of V/Z with increasing Ni content as long as ¦Ö<0.15, while V/Z has a small expansion when the Ni content ¦Ö>0.15. In compounds with a Ni-doping content greater than 0.2, an impurity phase, NiTa2O6, appears and increases its volume fraction significandy with increasing Ni content. It is known13 that the structural stability of oxides consisting of octahedra such as ABO3, can be estimated by calculating the tolerance factor defined as t=(rA+r0)/ (rB+r0)£¬where rA, rB and r0 are the radii of the respective ions. 0.79 |
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