Induced Manipulation of Atomically Dispersed Cobalt through S Vacancy for Photocatalytic Water Splitting: Asymmetric Coordination and Dynamic Evolution

It is still a challenge to construct single‐atom level reduction and oxidation sites in single‐component photocatalyst by manipulating coordination configuration for photocatalytic water splitting. Herein, the atomically dispersed asymmetric configuration of six‐coordinated Co‐S 2 O 4 (two exposed S atoms, two OH groups, and two Co─O─Zn bonds) suspending on ZnIn 2 S 4 nanosheets verified by combining experimental analysis with theoretical calculation, is applied into photocatalytic water splitting. The Co‐S 2 O 4 site immobilized by Vs acts as oxidation sites to guide electrons transferring to neighboring independent S atom, achieving efficient separation of reduction and oxidation sites. It is worth mentioning that stabilized Co‐S 2 O 4 configuration show dynamic structure evolution to highly active Co‐S 1 O 4 configuration (one exposed S atom, one OH group, and three Co─O─Zn bonds) in reaction, which lowers energy barrier of transition state for H 2 O activization. Ultimately, the optimized photocatalyst exhibits excellent photocatalytic activity for water splitting (H 2 : 80.13 µmol g −1 h −1 , O 2 : 37.81 µmol g −1 h −1 ) and outstanding stability than that of multicomponent photocatalysts due to dynamic and reversible evolution between stable Co‐S 2 O 4 configuration and active Co‐S 1 O 4 configuration. This work demonstrates new cognitions on immobilized strategy through vacancy inducing, manipulating coordination configuration, and dynamic evolution mechanism of single‐atom level catalytic site in photocatalytic water splitting.