Bio‐Inspired Hierarchical Nanoreactor With Hetero‐Coordinated Fe–P–Co Bridges for Whole‐Pathway‐Regulated Electrocatalytic Oxygen Reduction

Abstract

ABSTRACT Efficient oxygen reduction reaction (ORR) requires coordination of oxygen adsorption, transport, and catalysis at active sites. Yet most studies address only one step, overlooking whole‐pathway O 2 regulation and thus limiting performance. Here, we report a bioinspired Co‐doped Fe 2 P on N‐doped carbon featuring a hierarchical eucalyptus‐like nanoarchitecture, engineered to regulate oxygen throughout the electrochemical cycle, where Fe–P–Co hetero‐coordinated bridges anchored to the carbon substrate through Fe─N bonds induce strong electronic coupling and polarization. The hierarchical structure generated local electric fields that enriched OH − and O 2 , while multilevel porosity accelerated oxygen transport. This enabled coordinated optimization of oxygen adsorption, transfer, and active‐site electronic configuration. This nanohybrid achieved a half‐wave potential of 0.938 V vs. RHE, sustained discharge in Al‐air batteries for 373 h, and delivered an energy density of 3487 Wh/kg. Theoretical simulations revealed that Co‐doping shortened Fe─P bonds and tuned the Fe electronic environment, lowering the d‐band center and weakening Fe 3d‐O 2p interactions, which reduced the *OH desorption barrier and accelerated ORR kinetics. In situ Raman spectroscopy revealed that Fe–P–Co bridges served as active centers facilitating *OH release during ORR. These findings indicate that integrating hierarchical architecture, hetero‐coordinated Fe–P–Co bridges, and electronic‐state modulation enables whole‐pathway O 2 management for efficient oxygen electrocatalysis.