Vacancy‐Defect Single‐Atom Catalysts for Tandem CO₂ Electroreduction and Carbonylation Reactions from Flue Gas

Abstract Tandem CO 2 reduction with carbonylation reactions represents a promising approach to convert greenhouse gases into valuable chemicals. Herein, we propose a universal “N/O mixed pre‐coordination pyrolysis” strategy to construct vacancy‐defect single atom catalysts (Ni 1 ‐, Mn 1 ‐, Fe 1 ‐, Co 1 ‐, and Cu 1 ‐NC) with M‐N 3 coordination microenvironment. This vacancy‐defect endows Ni 1 ‐NC with excellent performance for CO 2 electroreduction, achieving a CO faradaic efficiency exceeding 90% across a wide range of current densities up to 300 mA cm −2 . The generated CO was directly fed to carbonylation reactions, producing organic chemicals with yields of up to 91.7% and leading to produce 1.13 g of benzophenone in a single run. For the first time, the membrane separation CO 2 system was integrated with tandem catalytic system, enabling direct utilization of flue gas for benzophenone synthesis with a 76.6% yield. This work offers a sustainable, eco‐friendly method for CO 2 separation and utilization by feeding industrial waste gas to carbonylation reactions.