▎ 摘　　要

The electrochemical CO2 reduction reaction (CO2RR) is a promising route for converting CO2 and excess renewable energy into valuable chemicals and synthetic fuels. Recently, carbon-based solid materials containing dopant-levels of transition metal and nitrogen (M-N-C) have emerged as a cost-effective, energy-efficient catalyst for the direct coreduction of CO, and H2O to CO. Fe-N-C catalysts are particularly interesting as they can reduce CO further to hydrocarbons. Despite these promising reports, the influence of the reaction conditions on the catalytic performance of Fe-N-C catalysts has not been addressed. Here, we study the role of the electrolyte on the CO2RR selectivity. Unlike hydrogen or methane generation, catalytic CO production is independent of the electrolyte pH on the normal hydrogen electrode potential scale, suggesting a decoupled elementary proton electron transfer mechanism for CO formation. The similarity between this heterogeneous charge-transfer reaction mechanism and that of molecular metal nitrogen porphyrin-type macrocyclic complexes strongly suggests that the carbon-embedded FeNx motifs of the solid-state electrocatalyst act as the primary catalytically active center and illustrates yet another example of unifying concepts between molecular and solid-state catalysis.