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要旨

We report novel structure–activity relationships and explore the chemical state and structure of catalytically active sites under operando conditions during the electrochemical CO₂ reduction reaction (CO₂RR) catalyzed by a series of porous iron–nitrogen–carbon (FeNC) catalysts. The FeNC catalysts were synthesized from different nitrogen precursors and, as a result of this, exhibited quite distinct physical properties, such as BET surface areas and distinct chemical N-functionalities in varying ratios. The chemical diversity of the FeNC catalysts was harnessed to set up correlations between the catalytic CO₂RR activity and their chemical nitrogen-functionalities, which provided a deeper understanding between catalyst chemistry and function. XPS measurements revealed a dominant role of porphyrin-like Fe–N_x motifs and pyridinic nitrogen species in catalyzing the overall reaction process. Operando EXAFS measurements revealed an unexpected change in the Fe oxidation state and associated coordination from Fe²⁺ to Fe¹⁺. This redox change coincides with the onset of catalytic CH₄ production around −0.9 V_RHE. The ability of the solid state coordinative Fe¹⁺–N_x moiety to form hydrocarbons from CO₂ is remarkable, as it represents the solid-state analogue to molecular Fe¹⁺ coordination compounds with the same catalytic capability under homogeneous catalytic environments. This finding highlights a conceptual bridge between heterogeneous and homogenous catalysis and contributes significantly to our fundamental understanding of the FeNC catalyst function in the CO₂RR.