Synergistically Modulating Electronic Structure and Interfacial Wettability of MnF 2 /NF−CNF Toward Enhanced Oxygen Reduction in Zinc−Air Batteries

Modulating the electronic structure and interfacial wettability of cathode catalysts is crucial for enhancing intrinsic activity and broadening triple‐phase interfaces for oxygen reduction reactions (ORR) in zinc−air batteries (ZABs), yet achieving their synergistic regulation faces a big challenge. Herein, an N/F source modulation strategy is proposed to synthesize porous carbon nanofibers anchored with MnF 2 nanocrystals and N/F heteroatoms (MnF 2 /NF−CNF). The unique interconnected fibrous and hierarchical porous architecture, together with tailored MnF 2 embedding and N/F doping, achieves an optimal balance between activity and wettability regulation. Excellent ORR performance with a high half‐wave potential of 0.87 V vs. RHE and limiting current density of 6.34 mA cm −2 is achieved, outperforming Pt/C and most previously reported Mn‐based/heteroatom‐doped systems. Theoretical and experimental analyses reveal surface N dopants as active sites, with MnF 2 modulating p‐orbital configuration, refining ORR pathways. Meanwhile, surface F dopants, in synergy with the porous architecture, regulate wettability, equilibrate electrolyte/oxygen transport, and substantially extend triple‐phase reaction interfaces. The assembled ZAB delivers an exceptional peak power density of 181.5 mW cm −2 with high specific capacity, rate capability, and cycling stability. This work deciphers the regulatory mechanism balancing catalytic activity and interfacial wettability, proving a versatile strategy for developing advanced ORR electrocatalysts in ZABs.