Simultaneous Capture of CO2 Boosting Its Electroreduction in the Micropores of a Metal–organic Framework

Abstract Integration of CO 2 capture capability from simulated flue gas and electrochemical CO 2 reduction reaction (eCO 2 RR) active sites into a catalyst is a promising cost‐effective strategy for carbon neutrality, but is of great difficulty. Herein, combining the mixed gas breakthrough experiments and eCO 2 RR tests, we showed that an Ag 12 cluster‐based metal–organic framework ( 1‐NH 2 , aka Ag 12 bpy‐NH 2 ), simultaneously possessing CO 2 capture sites as “CO 2 relays” and eCO 2 RR active sites, can not only utilize its micropores to efficiently capture CO 2 from simulated flue gas (CO 2 : N 2 =15 : 85, at 298 K), but also catalyze eCO 2 RR of the adsorbed CO 2 into CO with an ultra‐high CO 2 conversion of 60 %. More importantly, its eCO 2 RR performance (a Faradaic efficiency (CO) of 96 % with a commercial current density of 120 mA cm −2 at a very low cell voltage of −2.3 V for 300 hours and the full‐cell energy conversion efficiency of 56 %) under simulated flue gas atmosphere is close to that under 100 % CO 2 atmosphere, and higher than those of all reported catalysts at higher potentials under 100 % CO 2 atmosphere. This work bridges the gap between CO 2 enrichment/capture and eCO 2 RR.