Efficient charge separation and improved photocatalytic activity in Type-II & Type-III heterojunction based multiple...

The nanostructured, inner-coupled Bismuth oxyhalides (BiOX_0.5X'_0.5; X, X' = Cl, Br, I; X≠X') heterostructures were prepared using Quercetin (Q) as a sensitizer. The present study revealed the tuning of the band properties of as-prepared catalysts. The catalysts were characterized using various characterization techniques for evaluating the superior photocatalytic efficiency and a better understanding of elemental interactions at interfaces formed in the heterojunction. The material (BiOCl_0.5Br_0.5-Q) reflected higher degradation of MO (about 99.85%) and BPA (98.34%) under visible light irradiation than BiOCl_0.5I_0.5-Q and BiOBr_0.5I_0.5-Q. A total of 90.45 percent of total organic carbon in BPA was removed after visible light irradiation on BiOCl_0.5Br_0.5-Q. The many-fold increase in activity is attributed to the formation of multiple interfaces between halides, conjugated π-electrons and multiple -OH groups of quercetin (Q). The boost in degradation efficiency can be attributed to the higher surface area, 2-D nanostructure, inhibited electron-hole recombination, and appropriate band-gap of the heterostructure. Photo-response of BiOCl_0.5Br_0.5-Q is higher compared to BiOCl_0.5I_0.5-Q and BiOBr_0.5I_0.5-Q, indicating better light absorption properties and charge separation efficiency in BiOCl_0.5Br_0.5-Q due to band edge position. First-principles Density Functional Theory (DFT) based calculations have also provided an insightful understanding of the interface formation, physical mechanism, and superior photocatalytic performance of BiOCl_0.5Br_0.5-Q heterostructure over other samples.