Carrier confinement activated explicit solvent dynamic of CdS/BiVO4/H2O and optimized photocatalytic hydrogen evolution performances.

[Display omitted] • Photogenerated electrons are entirely located in BiVO 4 in CdS/BiVO 4. • CdS substrate in CdS/BiVO 4 /H 2 O can enhance hydrogen diffusing rate. • Used solvation effect can provide rational Δ G H* in HER process. • O p orbital reforms the orbital energy level and activates the HER activity. Herein, using an electrophoretic deposition strategy, a S-scheme CdS (cubic)/BiVO 4 (monoclinic) heterostructured photocatalyst is fabricated. The as-synthesized photocatalysts exhibit high carrier separation efficiency, prominent hydrogen evolution ability and high stability. The results of the detailed density functional theory (DFT) prove that the photogenerated electrons and holes are located in BiVO 4 and CdS components, respectively. Besides, an explicit solvent model based on the electron-enriched region in CdS/BiVO 4 heterojunction is designed deliberately to investigate the solid/liquid interface issues. Intriguing findings demonstrate that the surface hydrogen diffusing rate in CdS/BiVO 4 /H 2 O is faster than that of BiVO 4 /H 2 O and is highly associated with the electron-enrich effect, which has a greater capacity to promote water decomposition, the possibility of proton collision and photocatalytic hydrogen evolution. Notably, the H p orbital can participate in the electron-enrich effect during solvation, thus reforming the orbital energy level and activating the HER of the BiVO 4 component in the CdS/BiVO 4 system. [ABSTRACT FROM AUTHOR]