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

Mingfei Yu, Wei Chen, Qingqing Lin, Liuyi Li, Zheyuan Liu, Jinhong Bi, Yan Yu

2024Angewandte Chemie International Edition41 citationsDOIOpen Access PDF

Abstract

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.

Topics & Concepts

Ionic bondingSupramolecular chemistryCationic polymerizationElectrostaticsCovalent bondvan der Waals forceChemical physicsElectron transferChemistryExcited statePhotocatalysisPhotochemistryHydrogen bondCatalysisMaterials scienceNanotechnologyMoleculePhysical chemistryAtomic physicsPolymer chemistryOrganic chemistryIonPhysicsCovalent Organic Framework ApplicationsCO2 Reduction Techniques and CatalystsMetal-Organic Frameworks: Synthesis and Applications
Electrostatic Confinement‐Induced Excited Charge Transfer in Ionic Covalent Organic Framework Promoting CO<sub>2</sub> Reduction | Litcius