Electronic Structure Regulation of MnCo₂O₄ via Surface‐Phosphorization Coupling to Monolithic Carbon for Oxygen Electrocatalysis in Zn–Air Batteries

Abstract An urgent challenge to the development of rechargeable Zn–air batteries (RZABs) is the highly active, durable, and low‐cost catalysts for oxygen reduction reaction and oxygen evolution reaction (ORR and OER). Herein, a carbon‐based monolithic catalyst is designed via anchoring P‐modified MnCo₂O₄ inverse spinel nanoparticles on biomass‐derived carbon (P‐MnCo₂O₄@PWC). The introduction of surface P atoms regulates the electronic structures and valences of metal atoms by adjusting the coordination fields by (P‐O)^δ– and Metal‐P. The optimization of the adsorption behavior of key intermediates facilitates the activation and conversion of reaction species. The monolithic structure is beneficial to the construction of a three‐phase interface for efficient mass transfer and high electrical conductivity. The P‐MnCo₂O₄@PWC catalyst displays outstanding bifunctional catalytic properties with a thin ΔE (the difference between the OER potential at 10 mA cm^–2 and the ORR halfwave potential) of 0.66 V. The RZAB with P‐MnCo₂O₄@PWC as cathode delivers an exceptional peak power density (160 mW cm^–2) and remarkable cycle life (over 1200 cycles), overcoming those with noble metal counterparts. This research provides a promising general surface‐phosphorization way to the design of carbon electrocatalysts and the high‐value utilization of biomass.