Single‐Atom Co Meets Remote Fe for a Synergistic Boost in Oxygen Electrocatalysis

Abstract The oxygen electrocatalytic activity of transition metal catalysts can be tuned by tailoring their microstructure to optimize electronic configuration. Here, a one‐step Coordination‐Selective Synthesis strategy is developed to integrate Co single‐atom sites and Fe‐based nanoparticles within the same matrix, enabling long‐range electronic interactions that enhance Co‐N 4 reactivity and improve oxygen reduction reaction performance. X‐ray absorption spectroscopy confirmed that remote Fe‐based nanoparticles modulate the electron distribution at Co‐N 4 sites. Structural characterizations reveal that the optimal catalyst, Co 50% Fe 50% ‐NC, contains metallic Fe, Fe 3 O 4 , and Fe 4 N species. Electrochemical measurements show that it achieves onset and half‐wave potentials of 0.984 and 0.927 V versus RHE, surpassing Co 100% ‐NC with only Co‐N 4 sites. Additionally, it demonstrates efficient oxygen evolution reaction performance, achieving an overpotential of 298 mV at 20 mA cm −2 , comparable to RuO 2 . Density functional theory calculations reveal that Fe 4 N optimizes O‐containing intermediate adsorption/desorption, lowering the theoretical overpotential. Zn‐air batteries assembled with Co 50% Fe 50% ‐NC exhibited superior performance to Pt/C, highlighting its potential for bifunctional oxygen electrocatalysis. This study provides an approach for designing high‐performance catalysts by utilizing synergistic interactions between atomic and nanoscale metal species.