A Triad Photoanode for Visible Light?Driven Water Oxidation via Immobilization of Molecular Polyoxometalate on Polymeric Carbon Nitride

Due to their availability, low cost, nontoxicity, and tunability, polymeric carbon nitrides (CNx) represent one of the most attractive materials classes for development fully sustainable photo(electro)catalytic systems solar-driven water splitting. However, CNx-based photoanodes visible light-driven oxidation dioxygen is rather challenging, particularly due issues related photoelectrode stability effective coupling light absorber with catalysts. Herein, a triadic photoanode comprising porous TiO2 electron collector scaffold sensitized by CNx coupled molecular cobalt polyoxometalate (CoPOM = [Co4(H2O)2(PW9O34)2]10?) catalyst reported. Complete under (? > 420 nm) irradiation demonstrated, photocurrents down relatively bias potentials (0.2 V vs RHE). Furthermore, polyethyleneimine (PEI), cationic polymer shown act as an non-sacrificial electrostatic linker immobilization anionic CoPOM onto negatively charged surface CNx. The optimized deposition using PEI translates directly into improved efficiency transfer photogenerated holes molecules enhanced oxygen evolution. This work thus provides important design rules POM-based catalysts soft-matter photoelectrocatalytic architectures oxidation.