Designing and Engineering Atomically Dispersed Metal Catalysts for CO2 to CO Conversion: From Single to Dual Metal Sites

Abstract The electrochemical CO 2 reduction reaction (CO 2 RR) is a promising approach to achieving sustainable electrical‐to‐chemical energy conversion and storage while decarbonizing the emission‐heavy industry. The carbon‐supported, nitrogen‐coordinated, and atomically dispersed metal sites are effective catalysts for CO generation due to their high activity, selectivity, and earth abundance. Here, we discuss progress, challenges, and opportunities for designing and engineering atomic metal catalysts from single to dual metal sites. Engineering single metal sites using a nitrogen‐doped carbon model was highlighted to exclusively study the effect of carbon particle sizes, metal contents, and M−N bond structures in the form of MN 4 moieties on catalytic activity and selectivity. The structure‐property correlation was analyzed by combining experimental results with theoretical calculations to uncover the CO 2 to CO conversion mechanisms. Furthermore, dual‐metal site catalysts, inheriting the merits of single‐metal sites, have emerged as a new frontier due to their potentially enhanced catalytic properties. Designing optimal dual metal site catalysts could offer additional sites to alter the surface adsorption to CO 2 and various intermediates, thus breaking the scaling relationship limitation and activity‐stability trade‐off. The CO 2 RR electrolysis in flow reactors was discussed to provide insights into the electrolyzer design with improved CO 2 utilization, reaction kinetics, and mass transport.