Oxygen Vacancies Trigger Rapid Charge Transport Channels at the Engineered Interface of S‐Scheme Heterojunction for Boosting Photocatalytic Performance

Although oxygen vacancies (Ovs) have been intensively studied in single semiconductor photocatalysts, exploration of intrinsic mechanisms and in‐depth understanding of Ovs in S‐scheme heterojunction photocatalysts are still limited. Herein, a novel S‐scheme photocatalyst made from WO3‐Ov/In2S3 with Ovs at the heterointerface is rationally designed. The microscopic environment and local electronic structure of the S‐scheme heterointerface are well optimized by Ovs. Femtosecond transient absorption spectroscopy (fs‐TAS) reveals that Ovs trigger additional charge movement routes and therefore increase charge separation efficiency. In addition, Ovs have a synergistic effect on the thermodynamic and kinetic parameters of S‐scheme photocatalysts. As a result, the optimal photocatalytic performance is significantly improved, surpassing that of single component WO3‐Ov and In2S3 (by 35.5 and 3.9 times, respectively), as well as WO3/In2S3 heterojunction. This work provides new insight into regulating the photogenerated carrier dynamics at the heterointerface and also helps design highly efficient S‐scheme photocatalysts. A novel WO3‐Ov/In2S3 S‐scheme photocatalyst with advanced performance is developed. Rapid charge transport ways triggered by Ovs at the heterointerface are unveiled by femtosecond transient absorption spectroscopy (fs‐TAS). The mechanism of Ovs on this S‐scheme photocatalyst is revealed by comprehensive characterizations and theoretical calculations.