Atomically Dispersed Zr‐N Moieties Modulate Fe Coordination for Robust Oxygen Reduction Electrocatalysis

Abstract Iron‐nitrogen‐carbon (Fe‐N‐C) materials are promising non‐precious metal catalysts for the oxygen reduction reaction (ORR), yet their long‐term stability remains a critical challenge due to the dissolution of Fe‐based active sites and corrosion of the carbon support. Here, a Fe‐Zr dual‐atom carbon‐based catalyst (Fe,Zr‐NC) via a one‐step solid‐state synthesis method is reported. The introduction of atomically dispersed Zr–N units adjacent to Fe–N 4 centers creates a dual‐metal coordination structure that modulates the local electronic environment of Fe and weakens * OH adsorption, which is the rate‐limiting step in the ORR process. Density functional theory (DFT) calculations reveal that the Fe–Zr synergy positions the catalyst near the apex of the ORR activity volcano. Extended experimental EXAFS confirms a Fe–Zr distance of ≈3.30 Å, closely matching the theoretical optimum (≈3.39 Å). As a result, Fe, Zr‐NC achieves a high half‐wave potential (0.891 V vs reversible hydrogen electrode (RHE)) with negligible activity loss over 5000 cyclic voltammetry cycles, outperforming commercial Pt/C. In zinc–air batteries, the catalyst delivers a peak power density of 185.7 mW cm −2 and operates stably for over 453 h. This work highlights the importance of dual‐atom synergy in tuning intermediate binding energies and provides design principles for next‐generation ORR electrocatalysts.