Reinforcing Covalency via d–p–d Orbital Coupling Enables Dual-Site Selective Ozone Activation for Efficient CH <sub>3</sub> SH Mineralization
Rumeng Zhang, Jiahao Huang, Mengliang Hu, Muke Lin, Ji Mei, Shulin Zuo, Dehua Xia
Abstract
In catalytic ozonation systems, surface-adsorbed oxygen species (*O/*O 2 ) 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 0.5 Ni 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 *O 2 intermediates via t 2g –π* orbital interactions. This dual-site synergy enables 100% CH 3 SH mineralization at 600 000 mL h –1 g –1 with 24 h stability. It also sustains >95% CH 3 SH removal over 12 h under 75% relative humidity (attributed to weak H 2 O adsorption and enhanced hydrophobicity) while resisting sulfur poisoning through balanced Lewis acidity and high surface −OH density. Through in situ 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.