Construction of PdSe2/ZnIn2S4 heterojunctions with covalent interface for highly efficient photocatalytic hydrogen evolution

Constructing semiconductor heterojunctions can enable novel schemes for highly efficient photocatalytic activity. However, introducing strong covalent bonding at the interface remains an open challenge. Herein, ZnIn2S4 (ZIS) with abundant sulfur vacancies (Sv) is synthesized with the presence of PdSe2 as an additional precursor. The sulfur vacancies of Sv-ZIS are filled by Se atoms of PdSe2, leading to the Zn–In–Se–Pd compound interface. Our density functional theory (DFT) calculations reveal the increased density of states at the interface, which will increase the local carrier concentration. Moreover, the length of the Se-H bond is longer than that of the SH bond, which is good for the evolution of H2 from the interface. In addition, the charge redistribution at the interface results in a built-in field, providing the driving force for efficient separation of photogenerated electron-hole. Therefore, the PdSe2/Sv-ZIS heterojunction with strong covalent interface exhibits an excellent photocatalytic hydrogen evolution performance (4423 μmol g−1h−1) with an apparent quantum efficiency (λ > 420 nm) of 9.1 %. This work will provide new inspirations to improve photocatalytic activity by engineering the interfaces of semiconductor heterojunctions.