Elucidating the mechanistic origins of P dopants triggered active sites and direct Z-scheme charge transfer by P-MoS2@WO3 heterostructures for efficient photocatalytic hydrogen evolution

Highlights: • The doped nonmetal P elements provide abundant active sites on the stable basal (002) plane of MoS₂. • The heterojunction P-MoS₂@WO₃ provides an efficient thoroughfare to facilitate the separation of electron-hole pairs. • The optoelectronic transfer pathway with a direct Z-scheme charge mode at the interface of the P-MoS₂@WO₃ heterostructures. -- Abstract: MoS₂ has been proven to be an environmental-friendly and economic photocatalyst for clean energy generation. However, the energy conversion efficiency still needs to be more enhanced for practical application due to the limited number of active sites on the surface and the high recombination rate of electron-hole pairs. Herein, P-doping was utilized to increase the active sites, and the heterojunction was constructed with WO₃ to improve the charge separation rate. Our results show that the heterojunction P-MoS₂@WO₃ photocatalyst has a stable and durable photocatalytic activity in water splitting, which shows H₂ evolution rate of 73.8 μmol h^–1 g⁻¹. This good photocatalytic performance of P-MoS₂@WO₃ is attributed to increased active sites at the thermodynamically stable basal (002) plane of MoS₂ by the P-doping and the enhanced charge separation rate by the heterojunction with a direct Z-scheme mode. This study offers an efficient way to increase the active sites and separate charge carriers in MoS₂-based photocatalysts for H₂ generation.