A Chain‐Assembly Layered Polymer Toward Highly Effective Photosynthesis of Hydrogen Peroxide

As a metal‐free photocatalyst, polymeric carbon nitride (PCN) has garnered significant interest for the photosynthesis of H 2 O 2 . However, its further progress was strictly precluded by several intrinsic shortcomings, including a narrow light absorption range, poor charge separation/transportation efficiency, and harsh synthesis conditions. Herein, via a mild solvothermal method, we report a highly crystalline PCN‐like polymer (TpDt) with a unique chain‐assembly layered structure. Advantaged by the broad light absorption range, the enhanced charge separation and transportation, the improved hydrophilicity and proton conductivity, as well as the abundant active sites, TpDt exhibited outstanding photocatalytic performance with high H 2 O 2 production rates of 6499.1 µmol h −1 g −1 in pure water and 8047.8 µmol h −1 g −1 after protonation. Leveraging the keto‐enol tautomerization, TpDt also exhibited remarkable stability during photocatalytic processes. Beyond the conventional PCN, this work presents an ideal Tp‐based material platform with remarkable photoelectrochemical activity, opening a door for developing excellent polymeric photocatalysts.