Spin‐State Manipulation of Atomic Manganese Center by Phosphide‐Support Interactions for Enhanced Oxygen Reduction

Oxygen reduction reaction (ORR) kinetics are closely related to the electronic structure of active sites. Herein, a single-atomic Mn catalyst decorated with adjacent MoP nanocrystals (MoP@Mn_SAC-NC) is reported. The decoration of MoP drives the electronic structure transition of Mn sites from low-spin to high-spin states through an electronic phosphide-support interaction. The rearranged electron occupation in 3d_xz-yz and 3d_z ² orbitals of Mn sites leads to electrons occupying the σ orbital in Mn─*O₂, thereby favoring O₂ adsorption to initiate the ORR mechanism. In situ characterizations confirm that Mn 3d_z ² orbital occupation state can activate molecular O₂ and optimize the adsorption of the *OOH intermediate. As a result, the MoP@Mn_SAC-NC displays an outstanding alkaline ORR half-wave potential (E_1/2 = 0.894 V), excellent peak power densities (173/83 mW cm^-2 for liquid/solid-state Zn-air batteries, respectively), and long-term stability (840 h) superior to commercial Pt/C. This work provides profound insights into spintronics-level engineering, guiding the design of next-generation high-performance ORR catalysts.