Surface-modified, dye-sensitized niobate nanosheets enabling an efficient solar-driven Z-scheme for overall water splitting.

While dye-sensitized metal oxides are good candidates as H 2 evolution photocatalysts for solar-driven Z-scheme water splitting, their solar-to-hydrogen (STH) energy conversion efficiencies remain low because of uncontrolled charge recombination reactions. Here, we show that modification of Ru dye-sensitized, Pt-intercalated HCa 2 Nb 3 O 10 nanosheets ( Ru /Pt/HCa 2 Nb 3 O 10 ) with both amorphous Al 2 O 3 and poly(styrenesulfonate) (PSS) improves the STH efficiency of Z-scheme overall water splitting by a factor of ~100, when the nanosheets are used in combination with a WO 3 -based O 2 evolution photocatalyst and an I 3 - /I - redox mediator, relative to an analogous system that uses unmodified Ru /Pt/HCa 2 Nb 3 O 10 . By using the optimized photocatalyst, PSS/ Ru /Al 2 O 3 /Pt/HCa 2 Nb 3 O 10 , a maximum STH of 0.12% and an apparent quantum yield of 4.1% at 420 nm were obtained, by far the highest among dye-sensitized water splitting systems and comparable to conventional semiconductor-based suspended particulate photocatalyst systems.