Nanoarchitectonics on Z-scheme and Mott-Schottky heterostructure for photocatalytic water oxidation via dual-cascade charge-transfer pathways

The bottleneck for water splitting to generate hydrogen fuel is the sluggish oxidation of water. Even though the monoclinic-BiVO₄ (m-BiVO₄)-based heterostructure has been widely applied for water oxidation, carrier recombination on dual surfaces of the m-BiVO₄ component have not been fully resolved by a single heterojunction. Inspired by natural photosynthesis, we established an m-BiVO₄/carbon nitride (C₃N₄) Z-scheme heterostructure based on the m-BiVO₄/reduced graphene oxide (rGO) Mott-Schottky heterostructure, constructing the face-contact C₃N₄/m-BiVO₄/rGO (CNBG) ternary composite to remove excessive surface recombination during water oxidation. The rGO can accumulate photogenerated electrons from m-BiVO₄ through a high conductivity region over the heterointerface, with the electrons then prone to diffuse along a highly conductive carbon network. In an internal electric field at the heterointerface of m-BiVO₄/C₃N₄, the low-energy electrons and holes are rapidly consumed under irradiation. Therefore, spatial separation of electron-hole pairs occurs, and strong redox potentials are maintained by the Z-scheme electron transfer. These advantages endow the CNBG ternary composite with over 193% growth in O₂ yield, and a remarkable rise in ·OH and ·O₂⁻ radicals, compared to the m-BiVO₄/rGO binary composite. This work shows a novel perspective for rationally integrating Z-scheme and Mott-Schottky heterostructures in the water oxidation reaction.