期刊
ACS CATALYSIS
卷 11, 期 13, 页码 7890-7905出版社
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.1c00940
关键词
1,2-dichloroethane; hydrodechlorination; platinum catalyst; reaction kinetics; reaction mechanism; density functional theory; microkinetic model
资金
- Dow University Partner Initiative
- UW-Madison, under Dow [235744C]
- DOE-BES, Division of Chemical Sciences, Catalysis Science Program [DE-FG02-05ER15731]
- U.S. Department of Energy, Office of Science [DE-AC02-05CH11231]
- UW-Madison
- Advanced Computing Initiative
- Wisconsin Alumni Research Foundation
- Wisconsin Institute for Discovery
- National Science Foundation
Catalytic hydrodechlorination of 1,2-dichloroethane using Pt catalysts was studied through a synergistic approach of DFT calculations, reaction kinetics experiments, and microkinetic modeling. The reaction on Pt(111) involves multiple steps leading to the formation of ethane. Adjustments to model parameters were made to achieve good agreement between theoretical predictions and experimental results, highlighting the importance of coverage effects in catalytic reactions. Overall, the study provides valuable mechanistic insights for improving catalysts in this chemistry.
Catalytic hydrodechlorination is a promising strategy for treating industrial 1,2-dichloroethane wastes, for which Pt and Pt-based alloy catalysts are widely used. Here, we performed a detailed mechanistic study for 1,2-dichloroethane hydrodechlorination on Pt using a synergistic approach combining density functional theory (DFT) calculations, reaction kinetics experiments, and microkinetic modeling. Using planewave DFT calculations, we evaluated the reaction energy and activation energy barrier of each elementary step involved in the reaction network on Pt(111). The calculated energetics were then incorporated into a comprehensive mean-field microkinetic model accounting for a total of 65 elementary steps. The model-predicted reaction rates were compared with the results from our reaction kinetics experiments on SiO2-supported Pt catalysts. Our results indicated that the hydrodechlorination of 1,2-dichloroethane on Pt(111) starts with a H-removal step; then, it proceeds through a sequence of alternating dechlorination and dehydrogenation steps until vinylidene (CH2C*) is formed; finally, CH2C* is hydrogenated to the final product, ethane, sequentially via vinyl (CH2CH*), ethylene, and ethyl (CH3CH2*) intermediates. After model parameter adjustments, we achieved good agreement between our theoretical model and experimental results; the adjustments to the calculated parameters are consistent with the typically anticipated coverage effects. Our study offers valuable mechanistic insights, which are useful for improving catalysts for this chemistry.
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