Reinforcing Covalency via d–p–d Orbital Coupling Enables Dual-Site Selective Ozone Activation for Efficient CH ₃ SH Mineralization

In catalytic ozonation systems, surface-adsorbed oxygen species (*O/*O₂) have emerged as promising non-radical species. They exhibit high reactivity toward electron-rich pollutants and accelerate pre-oxidation via electron-transfer-driven mechanisms. However, their selective generation remains a critical challenge. Herein, we design an amorphous Co-Ni bimetallic oxide (Co_0.5Ni_0.5) with tailored Co(3d)-O(2p)-Ni(3d) orbital coupling, which synergistically enhances metal-oxygen covalency to optimize the bridge adsorption configuration of ozone molecules for efficient activation. The electron-rich Co sites, with optimized 3d e_g orbital occupancy, facilitate π backdonation to ozone, weakening O-O bonds for selective *O formation, while electron-deficient Ni sites stabilize *O₂ intermediates via t_2g-π* orbital interactions. This dual-site synergy enables 100% CH₃SH mineralization at 600 000 mL h^-1 g^-1 with 24 h stability. It also sustains >95% CH₃SH removal over 12 h under 75% relative humidity (attributed to weak H₂O adsorption and enhanced hydrophobicity) while resisting sulfur poisoning through balanced Lewis acidity and high surface -OH density. Through <i>in situ</i> spectroscopy and theoretical simulations, we demonstrate that d-p-d orbital hybridization governs both oxygen speciation and interfacial electron transfer kinetics. Our work establishes orbital-level engineering of bimetallic oxides as a universal strategy for sustainable volatile organic compound remediation.