Although high-valent metal hydroxyl oxides formed in situ through electrochemical oxidation of the metal oxide matrix are key active sites for the oxygen evolution reaction (OER) in transition metal oxides, such a sluggish structural reconstruction largely hinders the electrocatalytic performance. Herein, we present a novel spin polarization engineering strategy to accelerate the formation of high-valent CoOOH, thereby significantly enhancing the OER performance. Through strategic substitutional doping of Mn atoms into the CoO lattice and subsequent confinement of the resulting bimetallic oxides within hollow mesoporous carbon spheres (Mn-CoO/HMCS), the as-prepared catalyst demonstrates markedly enhanced electrocatalytic activity, delivering approximately 5.9-fold higher mass activity compared to the undoped CoO/HMCS counterpart. In situ spectroscopy and theoretical calculations elucidate that Mn doping induces lattice distortion and symmetry breaking, which alters the orbital filling of Co with a lower energy barrier for the structural reconstruction from Co²⁺ to Co³⁺. The spin state transition from a high-spin configuration in Co²⁺ to a low-spin state in Co³⁺ further facilitates the formation of CoOOH active intermediates for OER. This work not only paves new avenues for promoting the dynamic reconstruction of active hydroxyl oxides but also highlights the untapped potential of cobalt-based materials through rational electronic structure modulation.
