Catalytic mechanism and pathways of 1, 2-dichloropropane oxidation over LaMnO3 perovskite: An experimental and DFT study

Chuanhui Zhang; Haijie Cao; Chao Wang; Maoxia He; Wangcheng Zhan; Yanglong Guo

doi:10.1016/j.jhazmat.2020.123473

Catalytic mechanism and pathways of 1, 2-dichloropropane oxidation over LaMnO₃ perovskite: An experimental and DFT study

J Hazard Mater. 2021 Jan 15:402:123473. doi: 10.1016/j.jhazmat.2020.123473. Epub 2020 Jul 15.

Authors

Chuanhui Zhang¹, Haijie Cao², Chao Wang², Maoxia He³, Wangcheng Zhan⁴, Yanglong Guo⁵

Affiliations

¹ Institute of Materials for Energy and Environment, College of Materials Science and Engineering, Qingdao University, Qingdao, 266071, PR China; Key Laboratory for Advanced Materials and Research Institute of Industrial Catalysis, East China University of Science and Technology, Shanghai 200237, PR China. Electronic address: zhangch@qdu.edu.cn.
² Institute of Materials for Energy and Environment, College of Materials Science and Engineering, Qingdao University, Qingdao, 266071, PR China.
³ Environment Research Institute, Shandong University, Qingdao 266237, PR China.
⁴ Key Laboratory for Advanced Materials and Research Institute of Industrial Catalysis, East China University of Science and Technology, Shanghai 200237, PR China.
⁵ Key Laboratory for Advanced Materials and Research Institute of Industrial Catalysis, East China University of Science and Technology, Shanghai 200237, PR China. Electronic address: ylguo@ecust.edu.cn.

PMID: 32711383
DOI: 10.1016/j.jhazmat.2020.123473

Abstract

The rational comprehension on the catalytic mechanism and pathways of chlorinated volatile organic compounds (CVOCs) oxidation is meaningful for the design of high performance catalytic materials. Herein, we attempted to elucidate the catalytic mechanism and pathways of 1, 2-dichloropropane (1, 2-DCP) oxidation over LaMnO₃ perovskite from experimental and theoretical studies. Experimental results indicate that the initial dechlorination of 1, 2-DCP into allyl chloride (AC) can be readily achieved over LaMnO₃, while the further decomposition of AC is more vulnerable to be affected by the reaction conditions and strongly dependent on the surface active oxygen species. Density functional theory (DFT) calculation reveals that the heterogeneous conversion of 1, 2-DCP initiates with the chemisorption on the Mn site, followed by the formation of AC via a synergistic mechanism. AC decomposition is considered as the rate-determining step under an inert condition, while the dechlorination of adsorbed 1, 2-DCP dominates the whole reaction under an oxygen atmosphere.

Keywords: Catalytic oxidation; DFT calculation; Reaction pathway; Surface adsorbed oxygen.