Interfacial Mediation by Sn And S Vacancies of p‐SnS/n‐ZnIn2S4 for Enhancing Photocatalytic Hydrogen Evolution with New Scheme of Type‐I Heterojunction

Abstract

AbstractThe construction of interfacial electric field (IEF) in semiconductor heterojunction is of great significance in boosting photocatalytic hydrogen evolution through efficient separation of photogenerated charge‐carriers. However, the exploitation of IEF in type‐I heterojunction has not been proposed for designing photocatalysts. Herein, based on the density functional theory prediction, p‐SnS with different work functions modulated by Sn‐vacancy are compounded with n‐ZnIn2S4 containing S‐vacancy to form type‐I heterojunction. The optimized SnS/ZnIn2S4 photocatalyst without co‐catalysts exhibits an impressive hydrogen evolution rate of 22.75 mmol g−1 h−1, 6.23 times of ZnIn2S4. Systematic investigations reveal that the interfacial Sn‐S bond acts as a transport channel that accelerates the interface charge‐carriers transfer under the promotion of IEF originating from the significant Fermi level difference. A large difference in the surface photovoltage signal of SnS/ZnIn2S4 and ZnIn2S4 is achieved from effective photogenerated charge‐carriers separation by IEF. The new p‐n type‐I scheme of SnS/ZnIn2S4 induced by the interfacial mediation can separate the photogenerated charge‐carriers, and retain the highly reductive electrons of ZnIn2S4 for hydrogen evolution, overcoming the disadvantage of reduction potential decline in the typical type‐I scheme. This study will afford a new theoretical basis for the achievement of high‐efficiency photocatalytic hydrogen evolution through interface modulation.