Ultra-low Ag Loadings for CO2 Reduction via Tailored Molecular Electrocatalysts

Abstract Decreasing the catalytic loading and complexity of electrocatalysts for the reduction of CO2 is a critical necessity towards globally generating carbon-negative synthons. This effort therefore calls for the development of not only more active catalysts per employed g but also for more financially sound ones. Notably, molecular electrocatalysts allow for tuning the electronic and geometric environment around single-atom catalytic centers. Nevertheless, synthetic complexity, cost and electrochemical instability still hamper their large-scale implementation. With industrial application in mind, we herein present a holistic design approach starting from different Ag(I) N,N´-bis(arylimino)acenaphtene complexes to sophisticated architectures of electrolyzer components. Performed in industrially applicable cells at 60°C, this approach allows us to reach catalytic activity for CO formation close to 1 A cm-2, while achieving the highest mass activity reported for CO at 100.000 A gAg-1, accompanied by cost decreases up to a factor of 80 against the current heterogeneous standards. This study thus represents an unprecedented example to show the applicability of homogenous catalysts under industrially relevant conditions.