Abstract
Van der Waals heterostructures (vdWHs) showcase robust and tunable light-matter interactions, establishing an intriguing realm for investigating atomic-scale photocatalytic properties. Here, we employ ab initio methods to study the photocatalytic and optical properties of semiconducting SiPGaS/arsenene-based vdWHs with a type-II band alignment. Across the heterointerfaces, there exists significant built-in electric fields and large potential drop, in turn facilitating the spatial separation of photo-generated electron-hole pairs. These vdWHs further possess high carrier mobility in the order of 10(2) cm(2)V⁻(1)S⁻(1), which combining with appropriate band edge positions, endow the vdWHs an absorption coefficient of ∼10⁵ cm⁻(1) to harvest a maximal portion of the solar spectrum for visible-light-driven photocatalytic applications. Our findings also reveal transition of the type-II band alignment in a type-III configuration via compressive strain for tunneling field-effect transistor application. Furthermore, both types of vdWHs exhibit enhanced suitability for photocatalysis under conditions with a pH of 2.