Synergistic Adsorption and Magnetic Coupling Effects among Surface Atoms of P-Doped LaCoO₃ during the Oxygen Evolution Reaction Process

Elucidating the influence mechanism of doping on the catalytic performance of perovskite-type oxides is essential for the further development of perovskite-type oxides with high-performance oxygen evolution reaction (OER) catalysts. This study employs first-principles calculations to thoroughly investigate the OER pathways and underlying mechanisms of P-doped perovskite oxide LaCoO 3 . Results reveal that P doping modifies the coordination environment of surface Co atoms, concurrently bringing the Co-3d band center closer to the Fermi level and facilitating the transfer of electrons from the Co surroundings to adsorbed oxygen. These changes alter the adsorption characteristics of the *OH species and induce surface reconstruction. On this basis, a synergistic adsorption mechanism (SAM) among surface cobalt and lattice oxygen atoms is discovered during the OER reaction. Compared with the adsorption evolution mechanism (AEM) and lattice oxygen mechanism (LOM), the overpotential under the SAM pathway is only 0.24 V, with O 2 desorption being extremely facile. Furthermore, it is found that the magnetic coupling states during the reaction process play a significant role in further lowering the OER overpotential. These findings provide important theoretical insights and guidance for the design and development of high-performance perovskite-based OER catalysts.