Photocatalytic H₂O₂ production via oxygen reduction represents a sustainable pathway for solar-to-chemical  energy conversion. However, constructing sacrificial-agent-free heterojunctions that simultaneously maximize  charge separation and preserve redox ability remains a significant challenge. Herein, we report a molecular-level  interfacial engineering strategy to anchor COF-TpBpy onto CdSe nanorods via in-situ solvothermal growth,  fabricating a strongly coupled organic–inorganic S-Scheme heterojunction. Benefiting from the intimate inter facial contact, the optimized 10CdSe/TpBpy composite achieves a remarkable H₂O₂ yield of 4349 μmol⋅g−1·h⁻¹ in  pure water without any sacrificial agents, alongside an impressive apparent quantum yield (AQY) of 11.1% at  450 nm. Mechanistic investigations, combining Density Functional Theory (DFT) calculations, Kelvin probe force  microscopy (KPFM), and in-situ irradiated X-ray photoelectron spectroscopy (in-situ XPS), visually confirm a  robust built-in internal electric field (IEF) driven by the work function difference. Furthermore, femtosecond  transient absorption (fs-TA) spectroscopy reveals an ultrafast picosecond-scale interfacial charge transfer  behavior, providing direct kinetic evidence for the S-Scheme mechanism. This unique charge transfer pathway  effectively preserves the strong reducing electrons in the CdSe conduction band to boost the oxygen reduction  reaction (ORR) kinetics. This work offers a viable paradigm for designing robust hybrid S-Scheme architectures for efficient photocatalysis.

文章链接：https://doi.org/10.1016/j.apcatb.2026.127409

附件：10.1016j.apcatb.2026.127409.pdf