DFT Investigation of a Direct Z-Scheme Photocatalyst for Overall Water Splitting: Janus Ga2SSe/Bi2O3 Van Der Waals Heterojunction

Constructing van der Waals heterojunctions with excellent properties has attracted considerable attention in the field of photocatalytic water splitting. In this study, four patterns, coined A, B, C, and D of Janus Ga₂SSe/Bi₂O₃ van der Waals (vdW) heterojunctions with different stacking modes, were investigated using first-principles calculations. Their stability, electronic structure, and optical properties were analyzed in detail. Among these, patterns A and C heterojunctions demonstrate stable behavior and operate as direct Z-scheme photocatalysts, exhibiting band gaps of 1.83 eV and 1.62 eV. In addition, the suitable band edge positions make them effective for photocatalytic water decomposition. The built-in electric field across the heterojunction interface effectively inhibits electron-hole recombination, thereby improving the photocatalytic efficiency. The optical absorption coefficients show that patterns A and C heterojunctions exhibit higher light absorption intensity than Ga₂SSe and Bi₂O₃ monolayers, spanning from the ultraviolet to visible range. Their corrected solar-to-hydrogen (STH) efficiencies are 13.60% and 12.08%, respectively. The application of hydrostatic pressure and biaxial tensile strain demonstrate distinct effects on photocatalytic performance: hydrostatic pressure preferentially enhances the hydrogen evolution reaction (HER), while biaxial tensile strain primarily improves the oxygen evolution reaction (OER). Furthermore, the heterojunctions exhibited enhanced optical absorption across the UV-visible spectrum with increasing hydrostatic pressure. Notably, a 1% tensile strain results in an improvement in visible light absorption efficiency. These results demonstrate that Ga₂SSe/Bi₂O₃ heterojunctions hold great promise as direct Z-scheme photocatalysts for overall water splitting.