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

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.