Type-I band alignment of BX-ZnO (X = As, P) van der Waals heterostructures as high-efficiency water splitting photocatalysts: a first-principles study.

In this work, we perform first-principles calculations to examine the electronic, optical and photocatalytic properties of the BX-ZnO (X = As, P) heterostructures. The interlayer distance and binding energy of the most energetically favorable stacking configuration are 3.31 Å and -0.30 eV for the BAs-ZnO heterostructure and 3.30 Å and -0.25 eV for the BP-ZnO heterostructure. All the stacking patterns of the BX-ZnO heterostructures are proved to have thermal stability by performing AIMD simulations. The BAs-ZnO and BP-ZnO heterostructures are semiconductors with direct band gaps of 1.43 eV and 2.35 eV, respectively, and they exhibit type-I band alignment, which make them suitable for light emission applications with the ultra-fast recombination between electrons and holes. Both the BAs-ZnO and BP-ZnO heterostructures can exhibit a wider optical absorption range for visible-light owing to their reduced band gaps compared with the isolated BAs, BP and ZnO monolayers. The band alignment of both the BAs-ZnO and BP-ZnO heterostructures can straddle the water redox potential and they would have better performances owing to the direct band gap and the reduced band gap. All these findings demonstrate that the BX-ZnO heterostructures can be considered as potential photocatalysts for water splitting.