Engineering Proton Clamp Traps in Covalent Organic Frameworks for Boosting CO ₂ Capture and Photoreduction

Abstract

Abstract The targeted construction of efficient CO 2 capture platforms for photocatalysis remains a significant challenge. Herein, we precisely engineered a proton clamp within a series of covalent organic frameworks (COFs) to function as CO 2 traps, thereby significantly enhancing the photocatalytic reduction of CO 2 to CO. The proton clamp was rationally designed by using an S‐shaped molecular motif featuring appropriate interatomic distances and strategically positioned protonation sites. Remarkably, the protonated COFs exhibited a superior CO production rate of 109 µmol g −1 h −1 in a gas‐solid reaction condition. The experimental and theoretical investigations confirmed that the proton clamp not only facilitated efficient CO 2 trapping but also rapidly delivered protons to the active sites, accelerating the reaction kinetics. This work provides molecular‐level insights into protonation strategies for optimizing photocatalytic CO 2 reduction, offering a new design principle for advanced COF‐based photocatalysts.