Polymeric Carbon Nitride Edged with Spatially Isolated Donor and Acceptor for Sunlight‐Driven H₂O₂ Synthesis and In‐Situ Utilization

Abstract On‐site H 2 O 2 activation attracts much attention in energy conversion and environment remediation et al., yet remains challenging in its highly efficient and sustainable synthesis. Herein, we grafted a pair of spatially isolated donor (methoxyphenyl unit) and acceptor (anthraquinone unit) in polymeric carbon nitride edges, which induce directional electron‐hole transfer to the two spatially separated dual active centers. Specifically, photogenerated electrons in the anthraquinone unit facilitate the 2e − ORR, while the methoxyphenyl unit, which gathers photogenerated holes, enables rapid 4e − WOR. More impressively, the anthraquinone unit also exhibits strong proton extraction capabilities to boost the generation of *OOH intermediates and H 2 O 2 . Consequently, the synthesized donor‐polymeric carbon nitride‐acceptor (DPA) catalyst shows a remarkable H 2 O 2 yield of 6497.1 μ M h −1 g −1 in pure water, surpassing traditional DP and PA catalysts. Because of its high efficiency, the H 2 O 2 product can efficiently degrade and mineralize various organic contaminants in a continuous‐flow self‐Fenton reactor under sunlight irradiation. Our work presents an unprecedented approach to designing photocatalysts with efficient H 2 O 2 synthesis and practical application from a molecular engineering perspective.