Oxygen Vacancies Regulated S‐Scheme Charge Transport Route in BiVO 4 ‐OVs/g‐C 3 N 4 Heterojunction for Enhanced Photocatalytic Performance

Oxygen vacancies (OVs) are widely considered as active sites in photocatalytic reactions, yet the crucial role of OVs in S-scheme heterojunction photocatalysts requires deeper understanding. In this work, OVs at hetero-interface regulated S-scheme BiVO₄-OVs/g-C₃N₄ photocatalysts are constructed. The Fermi-level structures of BiVO₄ and g-C₃N₄ lead to a redistribution of charges at the heterojunction interface, inducing an internal electric field at the interface, which tends to promote the recombination of photogenerated carriers at the interface. Importantly, the introduction of OVs induces defect electronic states in the BiVO₄ bandgap, creating indirect recombination energy level that serves as crucial intermediator for photogenerated carrier recombination in the S-scheme heterojunction. As a result, the photocatalytic degradation rate on Rhodamine B (RhB) and tetracyclines (TCs) for the optimal sample is 10.7 and 11.8 times higher than the bare one, the photocatalytic hydrogen production rate is also improved to 558 µmol g^-1 h^-1. This work shows the importance of OVs in heterostructure photocatalysis from both thermodynamic and kinetic aspects and may provide new insight into the rational design of S-scheme photocatalysts.