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Sodium Tantalate Photocatalysts Doped with Metal Cations: Why Active for Water Splitting Reaction.

ChemSusChem 2019 Februrary 16
Sodium tantalate (NaTaO3) is the first semiconductor photocatalyst which produces hydrogen-oxygen mixed bubbles in the overall water splitting reaction, when properly doped with metal cations. A series of studies are reviewed here to answer the question of why doping with metal cations raised the quantum efficiency of the reaction. Infrared absorption of bandgap-excited photocatalysts demonstrated that cation doping reduced the electron-hole recombination rate and the steady-state population of charge carriers accordingly increased. In-depth studies are focused on Sr cations incorporated through the solid-state, flux, and hydrothermal reactions. It was revealed that the recombination rate was reduced when Ta cations were exchanged with Sr cations. Sodium cations were simultaneously exchanged to balance the cationic and anionic charges with no need for creating oxygen anion vacancies. NaTaO3-Sr(Sr1/3Ta2/3)O3 solid solution was formed as a result of the simultaneous doping. In addition to doping to the proper sites, the intra-particle distribution of Sr cations played an essential role to reduce the recombination rate. Strontium cations segregated to produce graded composition from the Sr-rich surface to the Sr-poor core. The bottom of the conduction band lifted up at the Sr-rich surface, and the excited electrons were driven to the Sr-poor core leaving holes at the surface. However, the graded composition had a double purpose; excited electron population increased and its fraction to contribute to the surface reaction decreased.

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