Comprehensive Summary Dual‐atom catalysts (DACs) show attractive prospects for the oxygen reduction reaction (ORR), yet face challenges in precise charge modulation that balances the activity and durability. Herein, we present a N,S‐coordinated Fe dual atomic catalyst modified by Fe 3 C nanoclusters (Fe 3 C/Fe 2 N x S) through pyrolyzing the mixtures of ZIF‐8‐encapsulated iron dimers and sulfur‐doped C 3 N 4 . Aberration‐corrected STEM and synchrotron X‐ray absorption spectroscopy (XAS) validated that the catalyst was composed of Fe dual atomic sites and Fe 3 C nanoclusters, in which Fe dual atoms were coordinated by five N atoms and one S atom. Fe 3 C/Fe 2 N x S exhibited excellent ORR activity in alkaline media, displaying a high half‐wave potential ( E 1/2 = 0.894 V vs . RHE) with near 4e – selectivity ( n = 3.92) and maintaining 86.8% retention after 20000 s, superior to commercial Pt/C. Impressively, the assembled zinc‐air battery delivered exceptional peak power density (163 mW·cm –2 ) and 200‐hour robust stability. Density functional theory (DFT) calculations revealed that electron transfer from Fe of Fe 2 N x S to neighboring Fe 3 C induced local charge asymmetry, shifting the d‐band center closer to Fermi level, thereby enhancing O 2 activation. Moreover, the OOH * formation energy barrier was reduced to 0.52 eV in Fe 3 C/Fe 2 N x S, accelerating ORR reaction kinetics. This work establishes nanocluster‐mediated electronic redistribution to tailor charge asymmetry for high‐performance electrocatalysts.
Lei et al. (Tue,) studied this question.