Establishing Dual-Interface Built-In Electric Fields within Janus Heterostructures for Cooperative Photoredox Catalysis

Rationally designing nanostructures and comprehensively understanding the structure–property relationships are important for directional charge transfer. A general dual-interface built-in electric field (BIEF) regulation strategy is developed to synthesize the bifunctional ZnS/Sv-chalcogenide/Ti3C2 heterostructure photocatalysts (Sv represents sulfur vacancies; chalcogenides include ZnIn2S4, CdS, and CdIn2S4) consisting of a ZnS/chalcogenide S-scheme heterojunction and a Sv-chalcogenide/Ti3C2 Schottky heterojunction. The ternary-component photocatalyst construction involves hollow core–shell heterostructure establishment via lateral epitaxy and chalcogenide-surface Ti3C2 nanoparticle introduction via a defect-mediated heterocomponent anchorage. These nanoreactors integrate the strong intrinsic driving force and enhanced interfacial electronic coupling, leveraging resulting dual-interface BIEFs for precise carrier mobility control and robust redox performance feedback. The BIEF-induced ultrafast charge transfer features powerful photocarrier enrichment and feeble photocarrier recombination at the ZnS/ZnIn2S4 S-scheme heterointerface as well as continuous steering of photocarrier localization and delocalized electron transport at the Sv-ZnIn2S4/Ti3C2 Schottky heterointerface. Simultaneously, BIEF-induced targeted molecule catalysis is marked by complementary adsorption and selective activation of key intermediates. Representative ZnS/Sv-ZnIn2S4/Ti3C2 demonstrates broad substrate compatibility and superhigh reactivity in cooperative biomass valorization and hydrogen evolution. This study provides a programmable framework for manipulating BIEFs by multicomponent ordered-space integration and interface engineering, elucidating the substantial impact of dual-interface BIEFs on carrier transport behavior and molecular catalytic behavior.