Point-to-Point Orientation Aligns P-Tailored Fe–N ₅ Motifs within Hierarchical Carbon Nanoreactors for Superior Oxygen Electrocatalysis in Zn–Air Batteries

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.