Exploring the effects of different crystal facet combinations and I-doping in the BiOCl/BiOI heterostructure on photocatalytic properties: a hybrid density functional investigation.

This study uses hybrid functional calculations to investigate the effects of various crystal facet combinations in BiOCl and BiOI on the photocatalytic activity of the BiOCl/BiOI heterostructure. The results show that the separation efficiencies of photo-generated electron-hole pairs in BiOCl(010)/BiOI(001) and BiOCl(010)/BiOI(010) are constrained by type I band alignments in principle. In contrast, BiOCl(001)/BiOI(001) and BiOCl(001)/BiOI(010) heterostructures, which operate under the direct Z-scheme type, exhibit an enhanced photo-generated charge separation efficiency, superior redox capacity, and enhanced visible light absorption. Specifically, BiOCl(001)/BiOI(010) exhibits a more remarkable reduction ability that can reduce O to ˙O. Furthermore, our investigations demonstrate that targeted I element doping in BiOCl(001)/BiOI(010) can reduce the band gap of the BiOCl(001) sheet, enhance visible light absorption, and maintain the direct Z-scheme characteristics, thereby further improving the photocatalytic performance. Additionally, we discovered that I doping can transform the BiOCl(010)/BiOI(001) heterostructure from type I into a direct Z-scheme heterostructure, resulting in a substantial enhancement in the separation efficiency and reduction ability of photo-generated carriers as well as visible light absorption with increasing I doping concentration. Considering the excellent charge injection efficiency observed in experiments with the BiOCl(010)/BiOI(001) heterostructure, I-BiOCl(010)/BiOI(001) may represent a superior photocatalyst. Thus, this study highlights the crucial and substantial roles of engineering specific crystal facet combinations and I doping in enhancing the photocatalytic performance of the BiOCl/BiOI heterostructure. This theoretical study contributes to the comprehension of related experimental findings and offers valuable insights for the development of novel BiOCl/BiOI heterostructures with superior photocatalytic activity.