Catalytic oxidation of model compounds for simulating dioxins: A molecular cutting method and kinetic study

Bin Li; Qinyuan He; Yongqi Zhao; Xue Li; Xiaolong Liu; Tingyu Zhu

doi:10.1016/j.jhazmat.2025.139209

Catalytic oxidation of model compounds for simulating dioxins: A molecular cutting method and kinetic study

J Hazard Mater. 2025 Jul 10:496:139209. doi: 10.1016/j.jhazmat.2025.139209. Online ahead of print.

Authors

Bin Li¹, Qinyuan He², Yongqi Zhao³, Xue Li³, Xiaolong Liu⁴, Tingyu Zhu³

Affiliations

¹ Faculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming 650500, China.
² Faculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming 650500, China; CAS Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China.
³ CAS Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China.
⁴ CAS Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China; Key Laboratory of Green and High-value Utilization of Salt Lake Resources, Chinese Academy of Sciences, Xining 810008, China. Electronic address: liuxl@ipe.ac.cn.

PMID: 40652847
DOI: 10.1016/j.jhazmat.2025.139209

Abstract

The catalytic oxidation test of highly-toxic dioxins have always been a difficult problem in the research process. In this study, a novel molecular cutting method was proposed to catalyze the oxidation of dioxins. polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) were cleaved into four organic compounds with secondary molecular structures, including chlorobenzene, benzofuran, 1,4-dioxane and furan, which is considered as a model pollutant for removing dioxin performance. The catalytic oxidation performance was evaluated using V/Ti, W/Ti, and VW/Ti supported on TiO₂. The experimental results showed that the VW/Ti catalyst exhibited the best catalytic performance, achieving complete conversion at 250 °C for chlorobenzene, 275 °C for benzofuran, and 175 °C for both 1,4-dioxane and furan. Kinetic studies revealed that the effect of pollutant concentration on the reaction rate was greater than that of oxygen concentration. The kinetic study shows that the influence of pollutant concentration is higher than that of oxygen concentration. Additionally, in-situ DRIFTS and Density Functional Theory (DFT) calculations confirmed that the C-O bond is cleaved first in the dioxin-catalyzed process, with CC bond cleavage serving as the rate-determining step.

Keywords: Catalytic oxidation; Dioxin; Kinetic studies; Molecular cutting method; VW/Ti.