Regulating Relative Nitrogen Locations of Diazine Functionalized Covalent Organic Frameworks for Overall H2O2 Photosynthesis

Abstract Nitrogen‐heterocycle‐based covalent organic frameworks (COFs) are considered promising candidates for the overall photosynthesis of hydrogen peroxide (H 2 O ). However, effects relative nitrogen locations remain obscured and photocatalytic performances COFs need to be further improved. Herein, a collection functionalized by various diazines including pyridazine, pyrimidine, pyrazine have been judiciously designed synthesized photogeneration H without sacrificial agents. Compared with pyrimidine pyrazine, pyridazine embedded in TpDz tends stabilize endoperoxide intermediate species, leading toward more efficient direct 2e ‐ oxygen reduction reaction (ORR) pathway. Benefiting from effective electron‐hole separation, low charge transfer resistance, high‐efficiency ORR pathway, an excellent production rate 7327 μmol g −1 h solar‐to‐chemical conversion (SCC) value 0.62 % has achieved TpDz, which ranks one best COF‐based photocatalysts. This work might shed fresh light on rational design functional targeting photocatalysts production.