Transient Dangling Active Sites of Fe(III)−N−C Single‐Atom Catalyst for Efficient Electrochemical CO ₂ Reduction Reaction

Abstract The Fe single‐atom catalyst (SAC) with an oxidation state of III anchored on the N‐doped carbon substrate (Fe(III)−N−C) delivers superior activity for catalyzing the electrochemical CO 2 reduction reaction (eCO 2 RR) to produce CO, but its mechanism remains contentious and the commonly adopted FeN 4 ‐C model is not a conformant model for Fe(III)−N−C but for Fe(II)−N−C. Herein, employing the grand‐canonical ensemble modeling with the density functional theory method benchmarked against the high‐level wavefunction theory method, we first identify the conformant model for Fe(III)−N−C to be FeN 1 C 3 ‐C, and we then unveil that the Fe(III)N 1 C 3 ‐C SAC generates a novel type of dangling active site transiently under working conditions, in which the Fe single‐atom leaves from the anchoring site by breaking all the Fe−C bonds but retains a stable binding to the substrate by the Fe−N bond. Thus, we further elucidate that this flexible dangling active site of Fe(III)−N−C renders a convoluted reaction network with facile CO 2 activation, which delivers superior activity for eCO 2 RR. Our findings provide a novel understanding of the structure–activity relationship for Fe−N−C and concrete insights into the design of highly active SACs.