Surface termination modulation for superior S-Scheme Bi2WO6/BiOI heterojunction photocatalyst: a hybrid density functional study

Abstract The prevailing theoretical frameworks indicate that depending on the growth conditions, the Bi 2 WO 6 (001) surface can manifest in three distinct terminations—DL-O–Bi (DL: double layers), O–Bi, and O–W. In this study, we conduct a comprehensive examination of the interplay between these terminations on Bi 2 WO 6 (001) and the 1I-terminated BiOI(001) facet, especially focusing on their impact on the photocatalytic activity of Bi 2 WO 6 /BiOI heterostructure, applying hybrid functional calculations. The models formulated for this research are designated as Bi 2 WO 6 (O–Bi)/BiOI(1I), Bi 2 WO 6 (DL-O–Bi)/BiOI(1I), and Bi 2 WO 6 (O–W)/BiOI(1I). Our findings reveal that Bi 2 WO 6 (O–Bi)/BiOI(1I) shows a type II band alignment, which facilitates the spatial separation of photo-generated electrons and holes. Notably, the Bi 2 WO 6 (DL-O–Bi)/BiOI(1I) configuration has the lowest binding energy and results in an S-scheme (or Step-scheme) heterostructure. In contrast to the type II heterostructure, this particular configuration demonstrates enhanced photocatalytic efficiency due to improved photo-generated carrier separation, augmented oxidation capability, and better visible-light absorption. Conversely, Bi 2 WO 6 (O–W)/BiOI(1I) presents a type I projected band structure, which is less conducive for the separation of photo-generated electron–hole pairs. In summation, this investigation points out that one could significantly refine the photocatalytic efficacy of not only Bi 2 WO 6 /BiOI but also other heterostructure photocatalysts by modulating the coupling of different terminations via precise crystal synthesis or growth conditions.