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

Nitrogen-heterocycle-based covalent organic frameworks (COFs) are considered promising candidates for the overall photosynthesis of hydrogen peroxide (H2O2). However, the effects of the relative nitrogen locations remain obscured and photocatalytic performances of COFs need to be further improved. Herein, a collection of COFs functionalized by various diazines including pyridazine, pyrimidine, and pyrazine have been judiciously designed and synthesized for photogeneration of H2O2 without sacrificial agents. Compared with pyrimidine and pyrazine, pyridazine embedded in TpDz tends to stabilize endoperoxide intermediate species, leading toward the more efficient direct 2e- oxygen reduction reaction (ORR) pathway. Benefiting from the effective electron-hole separation, low charge transfer resistance, and high-efficiency ORR pathway, an excellent production rate of 7327 μmol g-1 h-1 and a solar-to-chemical conversion (SCC) value of 0.62% has been achieved by TpDz, which ranks one of the best COF-based photocatalysts. This work might shed fresh light on the rational design of functional COFs targeting photocatalysts in H2O2 production.