Dual‐Channels Heterojunction Interface Engineering for Efficient Hydrogen Peroxide Photoproduction

ABSTRACT Photosynthesis of H 2 O 2 in pure water offers a sustainable alternative to the fossil‐dependent anthraquinone process, but its scalability is severely constrained by the rapid recombination of photogenerated charge carriers, even though construction of built‐in electric fields on semiconductor heterojunction with aligned energy band structure. Here we propose an interface engineering strategy that directs charge migration across semiconductor heterojunction through dual synergistic channels. By coupling π–π conjunction and hydrogen bond, it constructs a stable interfacial configuration that strengthens π–π interaction and establishes complementary electron and hole pathways to facilitate rapid and counter‐directed separation of electron and hole. Implemented in covalent organic frameworks/graphitic carbon nitride system, this strategy achieves record solar‐to‐H 2 O 2 performance: a synthesis rate of 13386 µmol h −1 g −1 , an apparent quantum yield of 22.1% at 420 nm, a solar‐to‐chemical energy conversion efficiency of 1.69% under simulated sunlight, and an ultralong stability up to 120 h in continuous‐flow operation, outperforming most state‐of‐the‐art photocatalysts. The designed interface engineering provides a general blueprint for constructing adaptive charge‐transfer architecture and advancing high‐efficiency photocatalytic system for scalable, carbon‐neutral solar‐to‐chemical production of clean fuels and oxidants.