Heterojunction interface of zinc oxide and zinc sulfide promoting reactive molecules activation and carrier separation toward efficient photocatalysis

Abstract

Heterojunction photocatalysts, which can alleviate the low carrier separation efficiency and insufficient light absorption capacity of a single catalyst, have received widespread attention. However, the specific interfacial structure of the heterojunction and its effect on the photocatalytic reaction is still unclear. Herein, a battery of zinc oxide/zinc sulfide (ZnO@ZnS) heterojunction microspheres with different degrees of sulfuration were successfully constructed via a facile hydrothermal method. The as-prepared photocatalysts shown decent aerobic nitric oxide (NO) oxidation performance under visible light irradiation, and the results of various characterization techniques illustrated that the superior photoactivity could be ascribed to the spatial separation of photoinduced electron-hole pairs due to the synergy of the internal electric field and the band offset. More importantly, density functional theory (DFT) calculations revealed that the heterojunction interface can significantly promote the generation of reactive oxygen species (ROS) and NO⁺ reaction intermediates and thus accelerate the photocatalytic reaction. Finally, in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) technology was used to time-dependently monitor the NO oxidation process, revealing the photocatalytic mechanism. This work investigated the role of the heterojunction interface in the gas-phase catalytic reaction, broadening the practical application of the ZnO@ZnS heterojunction.

Keywords: Activation of reactive molecules; Heterojunction interface; Reaction mechanism; Visible-light photocatalysis; ZnO@ZnS.