Enhancement in photocatalytic water splitting using van der Waals heterostructure materials based on penta-layers

Abstract

Recently, van der Waals heterostructures (vdWHs) have been used to improve the performance of 2D materials, enabling more applications. By using first-principles calculations, we have studied the electronic and optical properties of vdWHs composed of penta-siligraphene and other penta-layers (p-Si2C4/p-X; X = Si₂N₄, ZnO₂, Ge₂C₄ or SiGeC₄). The stability of the vdWHs is verified by computing their binding energy, vibrational phonon spectra and <i>ab initio</i> molecular dynamics simulations. By assessing the electronic properties, we have found that the p-Si2C4/p-ZnO2, p-Si2C4/p-Ge2C4 and p-Si2C4/p-SiGeC4 vdWHs are semiconductors with an indirect band gap characterized by type-I band alignment. Meanwhile, the p-Si2C4/p-Si2N4 vdWH is a quasi-direct band gap semiconductor characterized by type-II band alignment. Bader charge analysis and charge density of p-Si2C4/p-Si2N4 vdWHs showed that photogenerated electrons move from the p-Si2N4 monolayer to the p-Si2C4 monolayer limiting the recombination of photogenerated charges and improving the photocatalytic efficiency. Furthermore, the p-Si2C4/p-Si2N4 vdWH exhibits suitable band edge positions compared to isolated monolayers suggesting its potential applicability in photocatalytic water splitting. The calculated optical absorption revealed that the p-Si2N4 monolayer exhibits substantial optical absorption in the ultraviolet (UV) range, while the p-Si2C4 monolayer and the p-Si2C4/p-Si2N4 vdWH show outstanding optical absorption on the order of 10⁵ cm^-1 in the visible and UV ranges. More importantly, the p-Si2C4/p-Si2N4 vdWH can greatly improve the optical absorption in these regions, which leads to high-efficiency usage of solar energy. Our study provides a route to design new vdWHs based on pentagonal monolayers, as well as an efficient photocatalyst for photocatalytic water splitting and optical devices.