Surface modification of ZnIn(2)S(4) layers to realize energy-transfer-mediated photocatalysis

Photocatalytic selective aerobic oxidation reactions are crucial in designing advanced organic intermediates, but suffer from low conversion efficiency. Hence, activating O(2) to create suitable reactive oxygen species, such as singlet oxygen ((1)O(2)), can significantly increase the yield of desired products. Herein, using ZnIn(2)S(4) nanosheets as a model system, we build a surface-modified theoretical structure, where a surface-covered non-conductive macromolecular chain, polyvinyl pyrrolidone (PVP), is bound to ZnIn(2)S(4) and influences the O(2) adsorption process. PVP on the surface significantly changes the electronic structure and suppresses electron conduction of ZnIn(2)S(4) nanosheets. Therefore, abundantly photogenerated and long-lived species transfer their energy to physically absorbed O(2) to efficiently generate (1)O(2), which can oxidize sulphides into their corresponding sulphoxides. For sulphoxidation of different sulphides, surface modification brings a 3–9-fold increase in conversion efficiency and high selectivities ≥98%. This study provides a feasible way of boosting (1)O(2)-generation-related photocatalytic reactions.