Quantitative Construction of Boronic‐Ester Linkages in Covalent Organic Frameworks for the Carbon Dioxide Reduction

Abstract Covalent organic frameworks (COFs) have been utilized for catalyzing the reduction of carbon dioxide (CO2RR) due to their atomic metal centers and controllable pore channels, which are facilitated by different covalent bonds. However, the exploration of boron‐based linkages in these catalytic COFs has been limited owing to potential instability. Herein, we present the construction of boronic ester‐linked COFs through nucleophilic substitution reactions in order to catalyze the CO 2 RR. The inclusion of abundant fluorine atoms within the frameworks enhances their hydrophobicity and subsequently improves water tolerance and chemical stability of COFs. The content of boron atoms in the COF linkages was carefully controlled, with COFs featuring a higher density of boron atoms exhibiting increased electronic conductivity, enhanced reductive ability, and stronger binding affinity towards CO 2 . Consequently, these COFs demonstrate improved activity and selectivity. The optimized COFs achieve the highest activity, achieving a turnover frequency of 1695.3 h −1 and a CO selectivity of 95.0 % at −0.9 V. Operando synchrotron radiation measurements confirm the stability of Co (II) atoms as catalytically active sites. By successfully constructing boronic ester‐linked COFs, we not only address potential instability concerns but also achieve exceptional catalytic performance for CO 2 RR.