Premium
Covalent Organic Frameworks Enabling Site Isolation of Viologen‐Derived Electron‐Transfer Mediators for Stable Photocatalytic Hydrogen Evolution
Author(s) -
Mi Zhen,
Zhou Ting,
Weng Weijun,
Unruangsri Junjuda,
Hu Ke,
Yang Wuli,
Wang Changchun,
Zhang Kai A. I.,
Guo Jia
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202016618
Subject(s) - viologen , electron transfer , photochemistry , chemistry , photocatalysis , covalent bond , covalent organic framework , electron transport chain , cationic polymerization , photoinduced electron transfer , chemical engineering , organic chemistry , catalysis , biochemistry , engineering
Electron transfer is the rate‐limiting step in photocatalytic water splitting. Viologen and its derivatives are able to act as electron‐transfer mediators (ETMs) to facilitate the rapid electron transfer from photosensitizers to active sites. Nevertheless, the electron‐transfer ability often suffers from the formation of a stable dipole structure through the coupling between cationic‐radical‐containing viologen‐derived ETMs, by which the electron‐transfer process becomes restricted. Herein, cyclic diquats, a kind of viologen‐derived ETM, are integrated into a 2,2′‐bipyridine‐based covalent organic framework (COF) through a post‐quaternization reaction. The content and distribution of embedded diquat‐ETMs are elaborately controlled, leading to the favorable site‐isolated arrangement. The resulting materials integrate the photosensitizing units and ETMs into one system, exhibiting the enhanced hydrogen evolution rate (34600 μmol h −1 g −1 ) and sustained performances when compared to a single‐module COF and a COF/ETM mixture. The integration strategy applied in a 2D COF platform promotes the consecutive electron transfer in photochemical processes through the multi‐component cooperation.