Theoretical Insights into Metal-Fe@NC Dual-Atom Catalysts for Oxygen Reduction Reaction

Fe-N-C single-atom catalysts are among the most promising nonprecious electrocatalysts for the oxygen reduction reaction (ORR), yet their activity is constrained by the symmetric electronic structure of the Fe-N₄ moiety, which limits the tunability of oxygenated intermediate adsorption. Here we propose an electronic modulation strategy by coupling Fe-N₄ sites with main-group atoms to break this intrinsic symmetry. Using density functional theory calculations, 14 Fe-M@NC catalysts incorporating representative s- and p-block elements are investigated. Most main-group elements stabilize the Fe-N₄ motif and significantly reduce the ORR overpotential, with Fe-In@NC exhibiting a low value of 0.39 V. Free-energy analyses identify OH* protonation as the universal potential-determining step. Electronic structure analyses reveal that s/p-d orbital hybridization between the main-group metal and Fe atoms drives charge redistribution and d-band center modulation. An intrinsic electronic descriptor, Δεs/p→d, is proposed and correlates linearly with the ORR overpotential, providing a transferable principle for ORR catalyst design.