Overall Water Splitting under Visible Light through a Two‐Step Photoexcitation between TaON and WO₃ in the Presence of an Iodate–Iodide Shuttle Redox Mediator

A two-step, photocatalytic water splitting system consisting of Pt-loaded TaON (a H(2) evolution photocatalyst), Pt-loaded WO(3) (an O(2) evolution photocatalyst), and an iodate-iodide (IO(3)(-)/I(-)) shuttle redox mediator is investigated under visible light irradiation. Photocatalytic oxidation of water to O(2) and reduction of IO(3)(-) to I(-) proceeded with good selectivity over the Pt-WO(3) photocatalyst, even in the presence of a considerable amount of I(-) anions in the solution. The key difference between the adsorption properties of IO(3)(-) and I(-) anions on WO(3) strongly suggested that the photoexcited electrons could react efficiently with IO(3)(-) adsorbed on WO(3), whereas the photogenerated holes selectively reacted with water molecules owing to the low adsorptivity of I(-) on WO(3). Photocatalytic H(2) evolution on Pt-TaON proceeded efficiently, accompanied by I(-) oxidation to IO(3)(-) due to a substantial amount of adsorption of I(-) anions on the surface, whereas H(2) evolution was significantly inhibited by the competitive adsorption of IO(3)(-), which consumes photoexcited electrons. It was also found that WO(3) photocatalysts loaded with platinum oxide (PtO) showed a much higher activity for O(2) evolution in the presence of the electron acceptor IO(3)(-), compared to those loaded with Pt metal. Overall water splitting at a steady rate was demonstrated using a combination of Pt-TaON and Pt(PtO)-WO(3) in an aqueous NaI solution with neutral or weakly acidic pH values, where the concentration of NaI significantly affected the efficiency.