Perovskite‐Socketed Sub‐3 nm Copper for Enhanced CO2 Electroreduction to C2+

Abstract In situ socketing metal nanoparticles onto perovskite oxides has shown great potential in heterogeneous catalysis, but its employment in boosting ambient CO 2 electroreduction (CER) is unexplored. Here, a CER catalyst of perovskite‐socketed sub‐3 nm Cu equipped with strong metal–support interactions (SMSIs) is constructed to promote efficient and stable CO 2 ‐to‐C 2+ conversion. For such a catalyst, plentiful sub‐3 nm ellipsoid Cu particles are homogeneously and epitaxially anchored on the perovskite backbones, with concomitant creation of significant SMSIs. These SMSIs are able to not only modulate electronic structure of active Cu and facilitate adsorption/activation of key intermediates, but also to strengthen perovskite–Cu adhesion and intensify resistance to structural degradation. Beneficial from these advantageous merits, when evaluated in CER, it performs comparably to or better than most reported Cu‐based heteronanostructures. Relative to a physical‐mixture counterpart, it features marked improvements (up to 6.2 folds) in activity and selectivity for C 2+ , together with greatly boosted stability (>80 h). This work gives a new avenue to rationally design more advanced Cu‐based heteronanostructures for CER.