Electrostatic Confinement‐Induced Excited Charge Transfer in Ionic Covalent Organic Framework Promoting CO 2 Reduction

作者：Mingfei Yu, Wei Chen, Qingqing Lin, Liuyi Li, Zheyuan Liu, Jinhong Bi, Yan Yu · 发表于：Angewandte Chemie International Edition · 年份：2024 · DOI：10.1002/anie.202418422 · 被引用次数：47 · 研究领域：Covalent Organic Framework Applications、CO2 Reduction Techniques and Catalysts、Metal-Organic Frameworks: Synthesis and Applications

Abstract We demonstrate an electrostatic confinement‐induced charge transfer pathway in a supramolecular photocatalyst comprising of an ionic covalent organic framework (COF) and cationic metal complexes. The dynamic electrostatic interactions not only attract cations around the COF to accept photogenerated electrons, but also allow for a retention of homogeneous catalytic characters of complexes, making a subtle balance. Accordingly, the electrostatic confinement effect facilitates the forward electron transfer from a photoexcited COF to cationic Co complex, realizing a remarkable photocatalytic CO 2 reduction performance. Its catalytic efficiency is far superior to the supramolecular counterparts with Van‐der‐Waals or hydrogen bonding interactions. This work presents an insight for enhancing charge transfer in supramolecular systems, and provides an effective approach for construction of highly efficient photocatalysts.