Localized Asymmetric Carbon Nitride with Tailored Electronic Traps: Modulating Charge Kinetics to Promote Efficient Light‐Driven H 2 O 2 Production

ABSTRACT The development of artificial photosynthesis for hydrogen peroxide (H 2 O 2 ) production holds considerable practical significance in pivotal fields such as energy conversion and environmental remediation. However, the precise manipulation of photocatalyst electronic structures and the induction of directional photogenerated charge migration remain among the core challenges in this field. Herein, we realized accurate modulation of carbon (C) doping concentrations in carbon nitride (CN) matrices via the introduction of uracil during supramolecular self‐assembly. Based on the regulation of electronic structure and dipole moment, a localized asymmetric carbon nitride photocatalyst (KCCN V ) featuring customized electron traps has been designed and constructed. More importantly, by precisely constructing electronic traps (cyano groups, ─C≡N), novel localized electron‐rich domains are formed to efficiently capture photo‐generated electrons and induce directed carrier migration, thereby significantly suppressing the non‐radiative recombination of photo‐generated electron‐hole pairs. KCCN V achieved an impressive H 2 O 2 production efficiency of 6120.1 µmol g −1 h −1 under oxygen conditions. Furthermore, a Fenton reaction system using H 2 O 2 was constructed in the field to achieve efficient mineralization removal of organic wastewater. This work provides valuable insights into the future solar‐driven H 2 O 2 synthesis and its practical applications, via the rational design of localized asymmetric carbon nitride based on electronic structure engineering.