Super-exchange interaction enables Fe_2-xMn_xO₃ perovskite with excellent catalytic oxidation activity toward...

Although enhancing the catalytic oxidation activity is a hotspot in thermal-driven catalytic disposal of persistent organic pollutants, few studies have managed to improve catalysts' water-resistance properties. Herein, we developed Fe_2-xMn_xO₃ perovskite to boost the catalytic oxidation of hexabromocyclododecane under humidity by modulating its super-exchange interaction (SEI, Fe³⁺ + Mn³⁺ → Fe²⁺ + Mn⁴⁺). Fe_0.4Mn_1.6O₃, with the strongest SEI, exhibits the biggest oxidation rate-constant, which is 3 times higher than that of commonly used Fe₂O₃ without SEI. Notably, unlike Fe₂O₃ which deactivates at a relative humidity of 5 %. Fe_0.4Mn_1.6O₃ maintains its activity and is even boosted by 22 % compared to dry conditions. Mechanistic insights reveal that SEI between Fe and Mn enhances the reactivity of Mn⁴⁺- linked O_latt by lowering the reductive temperature from Mn⁴⁺ to Mn³⁺. Meanwhile, SEI promotes the adsorption of the associatively adsorbed H₂O (HOH-type water) by reducing adsorption energy, thereby facilitating the formation of hydroxyl species, which are crucial for the oxidation process under humidity.