The precise integration of atomically dispersed active sites into engineered carbon architectures for the oxygen reduction reaction (ORR) remains challenging. Herein, we introduce a novel point-to-point orientation strategy that enables the precise engineering of P-tailored Fe–N 5 motifs within raspberry-like hierarchical carbon nanoreactors (P/Fe–N–HCNCs) for oxygen electrocatalysis in Zn–air batteries. The deliberately designed hierarchical architecture ensures efficient three-dimensional mass transfer, guaranteeing access to active sites. The second-shell P-coordination tailors an electron-asymmetric environment around Fe, optimizing the adsorption free energy of *OOH intermediates and accelerating the ORR kinetics. Consequently, the P/Fe–N–HCNCs delivers an exceptional half-wave potential of 0.94 V vs RHE along with outstanding stability. When deployed in a Zn–air battery, it achieves a peak power density of 271.4 mW cm –2 and an impressive specific capacity of 816 mA h g –1, surpassing most reported nonprecious metal catalysts. This work establishes a general design principle synergizing atomic coordination and nanoarchitecture engineering.
Tan et al. (Mon,) studied this question.