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| - Zinc Germanium Oxynitride as a Photocatalyst for Overall Water Splitting under VisibleLight
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| - A solid solution of zinc oxide and germanium nitride (Zn1+xGe)(N2Ox) (x = 0.44) is demonstrated to be aneffective photocatalyst for overall water splitting under ultraviolet and visible light. The catalyst is preparedby reaction of GeO2 and ZnO under ammonia flow (20 mL·min-1) at 1123 K for 15 h. The crystal structureof the material is investigated by a combination of Rietveld analysis and the maximum-entropy method usingneutron powder diffraction data. The (Zn1.44Ge)(N2.08O0.38) catalyst is confirmed to have a wurtzite-type structure(space group P63mc) and to be the solid solution where the oxygen atoms are substituted for nitrogen atoms.The (Zn1.44Ge)(N2.08O0.38) catalysts thus prepared exhibit a band gap of ca. 2.7 eV and corresponding activityat visible wavelengths. The decrease in band gap compared to the starting materials is attributed to largervalance band dispersion resulting from the energy difference between O2p and N2p orbitals and from thep−d repulsion between Zn3d and N2p+O2p electrons in the upper valance band, which raises the top of thevalance band. (Zn1.44Ge)(N2.08O0.38) powder modified by surface loading with RuO2 nanoparticles at 5 wt %achieves overall water splitting under both ultraviolet and visible irradiation.
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