Defect-Enriched ZnO/ZnS Heterostructures Derived from Hydrozincite Intermediates for Hydrogen Evolution under Visible Light.

Introducing defect engineering into ZnO/ZnS heterojunction photocatalysts is an effective method to simultaneously improve their visible light performance and photocatalytic efficiency. Herein, a defect-enriched ZnO/ZnS heterostructure photocatalyst was synthesized through a hydrozincite [Zn 5 (OH) 6 (CO 3 ) 2 ] intermediate-deriving reaction. The mechanism analysis showed that there were interstitial Zn and Zn vacancies in the hydrozincite-derived ZnO, while S vacancies and interstitial S and Zn vacancies were formed in ZnS components after calcination. These specific defect states endowed visible light response ability to both ZnO and ZnS components in the ZnO/ZnS photocatalysts. Under visible light irradiation, the photocatalytic hydrogen evolution rate of ZnO/ZnS reached 11.68 mmol h -1  g -1 , and under simulated sunlight irradiation, the best photocatalytic hydrogen evolution rate could reach 27.94 mmol h -1  g -1 , which was much higher than most previous reports. The analysis of energy band structure and photodeposition showed that the photocatalytic reduction sites were mainly on ZnS, and the photocatalytic reaction mainly followed the typical Z-type mechanism. This work presents a simple and low-cost method for the preparation of defects-enriched ZnO/ZnS-based photocatalytic materials with high photocatalytic activity and stability.