Chelated Linkage and Framework Isomerism Effect Toward Robust Zn‐Salen MCOFs for Dual‐Channel Overall H <sub>2</sub> O <sub>2</sub> Photosynthesis
Yue Chen, Tao Yang, Yaowei Jin, Jiaxin Li, Junlin Gu, Xiaojing Sun, Yingying Zou, Rui Liu, Guangfeng Wei, Chengzhong Yu, Aiguo Kong
Abstract
Abstract It remains challenging to synthesize effective and photocorrosion‐tolerated organic photocatalysts for two‐electron oxygen reduction reaction (2e⁻ ORR) and water oxidation reaction (2e⁻ WOR). Herein, two isomeric Zn‐Salen metal covalent organic frameworks (Zn‐Salen‐MCOFs) with kgd‐v or hcb topology are designed as robust and efficient photocatalysts for dual‐channel H 2 O 2 photosynthesis. Zn‐Salen‐MCOF with kgd‐v topology shows a higher H 2 O 2 photocatalytic production rate of 6617/3438 µmol gcat. −1 h −1 in pure water with/without additional O 2 or air saturation, together with long‐time continuous H 2 O 2 photosynthesis performance (100 h). The framework isomerism effect and the chelated linkages contribute to the improved H 2 O 2 photosynthesis efficiency and stability of it. A three‐step 2e⁻ WOR with the initial H 2 O adsorption over the ZnO 2 N 2 unit and a four‐step 2e⁻ ORR reaction mechanism with the key H ad adsorption at the pyrazinic N site are proposed. This study paves the way for developing robust MCOF‐based photocatalysts for dual‐channel H 2 O 2 production based on chelated linkage and framework isomerism effect.