Herein, we demonstrate a sodium/molybdenum (Na/Mo) co-doped ferroelectric PbTiO3 for efficient photocatalysis under visible light. Doped with high concentration of Mo6+, quasi-continuous new energy levels are successfully introduced below the conduction band minimum of PbTiO3, giving rise to a band-to-band redshift of the absorption edge. The valence state difference of Mo6+ and Ti4+ in the doped PbTiO3 is compensated by the Na dopant, thus effectively suppressing the formation of the recombination centres caused by Mo4+. Combined with the intrinsic built-in electric field in PbTiO3, this Na/Mo co-doping strategy enables PbTiO3 superior water oxidation activity under visible light with threshold wavelength up to 550 nm, which also promotes the efficient overall water splitting under visible light in a Z-scheme photocatalytic system. The strategy developed here provides a generally applicable solution to extend the visible light absorption spectrum and engineer electronic structures of ferroelectric materials for photocatalysis and other energy conversion applications.

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