Synergies of Fe Single Atoms and Clusters on N‐Doped Carbon Electrocatalyst for pH‐Universal Oxygen Reduction

Abstract Single atomic metal–N–C materials have attracted immense interest as promising candidates to replace noble metal‐based electrocatalysts for the oxygen reduction reaction (ORR). The coordination environment of metal–N–C active centers plays a critical role in determining their catalytic activity and durability, however, attention is focused only on the coordination of metal atoms. Herein, Fe single atoms and clusters co‐embedded in N‐doped carbon (Fe/NC) that deliver the synergistic enhancement in pH‐universal ORR catalysis via the four‐electron pathway are reported. Combining a series of experimental and computational analyses, the geometric and electronic structures of catalytic sites in Fe/NC are revealed and the neighboring Fe clusters are shown to weaken the binding energies of the ORR intermediates on Fe–N sites, hence enhancing both catalytic kinetics and thermodynamics. This strategy provides new insights into the understanding of the mechanism of single atom catalysis.