Electron Bridge Effect Induced by Oxygen-Bridged Co on MnFe Core-Shell Sphere for Boosting Catalytic Ozonation of...

Catalytic ozonation technology occupies a pivotal position in the treatment of chlorinated volatile organic compounds (Cl-VOCs) owing to its mild reaction conditions and exceptional efficiency. However, the efficacy of catalytic ozonation remains governed by the electronic properties and interfacial interactions of the catalyst. It constitutes a formidable challenge to improve chlorine poisoning resistance while preserving efficient electron transfer. In this study, cobalt (Co) was introduced into the MnFeO framework via in situ engineering to yield a MnFeO-Co_0.02(F) catalyst with Co-O-Mn/Fe. Through catalytic ozonation, the catalyst maintained 100% 1,2-DCE conversion and over 95% mineralization within 50 h, outperforming reported catalysts. Mechanistic studies showed that Co-O-Mn/Fe modulated the local electronic environment, inducing differentiated shifts in the d- and p-band centers and forming an interfacial electron bridge between the Mn-rich shell and Fe-rich core. This accelerated electron transfer reduced the energy barrier of the rate-determining step in O₃ activation and promoted reactive oxygen species generation. Additionally, the Co-O-Mn/Fe stabilized the catalyst surface, facilitated chlorine species migration, and suppressed metal chloride formation, thereby enhancing chlorine resistance. This work provides insights into designing high-performance catalysts with efficient O₃ activation and durability, promoting practical catalytic ozonation of Cl-VOCs.