Regulating Relative Nitrogen Locations of Diazine Functionalized Covalent Organic Frameworks for Overall H 2 O 2 Photosynthesis

• Published in: Angewandte Chemie International Edition Vol. 62; no. 41
• Main Authors: Liao, Qiaobo, Sun, Qiannan, Xu, Haocheng, Wang, Yandong, Xu, Yang, Li, Ziyu, Hu, Jinwu, Wang, Ding, Li, Huijun, Xi, Kai
• Format: Journal Article
• Language: English
• Published: 09-10-2023
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202310556

Abstract
Nitrogen‐heterocycle‐based covalent organic frameworks (COFs) are considered promising candidates for the overall photosynthesis of hydrogen peroxide (H
2
O
2
). 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 H
2
O
2
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 H
2
O
2
production.