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

ABSTRACT: 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 inter

SUBMITTER: Luo Z 

PROVIDER: S-EPMC12288810 | biostudies-literature | 2025 Jul

REPOSITORIES: biostudies-literature