Abstract
Hydrogenases (H(2) ases) are benchmark electrocatalysts for H(2) production, both in biology and (photo)catalysis in vitro. We report the tailoring of a p-type Si photocathode for optimal loading and wiring of H(2) ase through the introduction of a hierarchical inverse opal (IO) TiO(2) interlayer. This proton-reducing Si|IO-TiO(2) |H(2) ase photocathode is capable of driving overall water splitting in combination with a photoanode. We demonstrate unassisted (bias-free) water splitting by wiring Si|IO-TiO(2) |H(2) ase to a modified BiVO(4) photoanode in a photoelectrochemical (PEC) cell during several hours of irradiation. Connecting the Si|IO-TiO(2) |H(2) ase to a photosystem II (PSII) photoanode provides proof of concept for an engineered Z-scheme that replaces the non-complementary, natural light absorber photosystem I with a complementary abiotic silicon photocathode.