Super-exchange interaction enables Fe2-xMnxO3 perovskite with excellent catalytic oxidation activity toward hexabromocyclododecane under humidity

Mingge Wu; Cheng Chen; Jia Duo; Qianqian Li; Maoyong Song; Bohua Sun; Guijin Su

doi:10.1016/j.jhazmat.2024.135691

Super-exchange interaction enables Fe_2-xMn_xO₃ perovskite with excellent catalytic oxidation activity toward hexabromocyclododecane under humidity

J Hazard Mater. 2024 Nov 5:479:135691. doi: 10.1016/j.jhazmat.2024.135691. Epub 2024 Aug 28.

Authors

Mingge Wu¹, Cheng Chen¹, Jia Duo², Qianqian Li¹, Maoyong Song¹, Bohua Sun¹, Guijin Su³

Affiliations

¹ Key Laboratory of Environmental Nanotechnology and Health Effects, and State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China; University of Chinese Academy of Sciences, Beijing 100049, China.
² Xinjiang Key Laboratory of Environmental Pollution and Bioremediation, Xinjiang Institute of ecology and geography, Chinese Academy of Sciences, Urumqi, Xinjiang 830011, China.
³ Key Laboratory of Environmental Nanotechnology and Health Effects, and State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China; University of Chinese Academy of Sciences, Beijing 100049, China. Electronic address: gjsu@rcees.ac.cn.

PMID: 39217925
DOI: 10.1016/j.jhazmat.2024.135691

Abstract

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.

Keywords: Catalytic oxidation; Fe(2−x)Mn(x)O(3) perovskite; Persistent organic pollutants; Super-exchange interaction; Water-resistance.