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

On-site H₂O₂ 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 H₂O₂. Consequently, the synthesized donor-polymeric carbon nitride-acceptor (DPA) catalyst shows a remarkable H₂O₂ yield of 6497.1 μM h^-1 g^-1 in pure water, surpassing traditional DP and PA catalysts. Because of its high efficiency, the H₂O₂ 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 H₂O₂ synthesis and practical application from a molecular engineering perspective.