Synchronous Increase in Spin‐State Induced by Advanced 3 <i>d</i> –4 <i>d</i> Orbital Hybridization for Enhancing Radical Yield

Abstract The development of Fenton‐like catalysts with efficient interfacial electron transfer abilities is a critical challenge in peroxymonosulfate (PMS)‐based Fenton‐like reactions for water remediation. Herein, the synthesis of a series of Mo‐doped Co 3 O 4 catalysts ( x %Mo–Co 3 O 4 ) is reported via the controlled pyrolysis of precursors with remarkable enhancement in PMS activation. X‐ray absorption fine structure spectroscopy and theory calculations demonstrate that Mo 6+ preferentially substitutes octahedrally coordinated Co 3+ sites, generating additional oxygen vacancies. Significantly, the bimetallic synergy facilitates directional electron transfer from Co 2+ and Co 3+ to Mo 6+ via 3 d –4 d orbital hybridization, concurrently increasing the spin states of both metal centers and modulating the Co d ‐band center from 0.14 to −0.29 eV. This electronic modulation optimizes PMS adsorption and interfacial electron transfer on 2%Mo–Co 3 O 4 . Consequently, the yields of sulfate and hydroxyl radicals catalyzed by 2%Mo–Co 3 O 4 /PMS are 20.5 and 13.0 fold higher than those catalyzed by Co 3 O 4 /PMS, respectively. 2%Mo–Co 3 O 4 /PMS demonstrates excellent long‐time treatment ability (≈104 h), positive environmental impacts, and economic benefits, as revealed by continuous reactor, toxicity analysis, and life cycle assessments. Overall, this study elucidates the pivotal role of asymmetric bimetallic orbital hybridization in Fenton‐like reactions, providing a design blueprint for high‐performance materials for environmental remediation.