Manganese-Substituted Polyoxometalate as an Effective Shuttle Redox Mediator in Z-Scheme Water Splitting under Visible Light.

In the present study, a polyoxometalate is for the first time applied as a shuttle redox in two-step (Z-Scheme) photocatalytic water splitting. Photocatalytic H2 evolution using a Mn-substituted polyoxometalate [SiW11 O39 Mn(II) (H2 O)](6-) as an electron donor proceeded over a Ru-loaded SrTiO3 :Rh photocatalyst under visible light with relatively high selectivity, accompanied by the stoichiometric production of its oxidized form [SiW11 O39 Mn(III) (H2 O)](5-) . Photocatalytic O2 evolution using the oxidized [SiW11 O39 Mn(III) (H2 O)](5-) as an electron acceptor proceeded over PtOx -loaded WO3 photocatalyst under visible light with relatively high quantum efficiency and selectivity, whereas the loading of effective PtOx cocatalyst was necessary to facilitate the reduction of polyoxometalate. Finally, a two-step water splitting into H2 and O2 was demonstrated under visible light using the couple of Mn-substituted polyoxometalate as shuttle redox between Ru/SrTiO3 :Rh and PtOx /WO3 photocatalysts, under mildly acidic conditions with pH≈4.5.