Hydrodechlorination of 1,2-Dichloroethane on Platinum Catalysts: Insights from Reaction Kinetics Experiments, Density Functional Theory, and Microkinetic Modeling

Xu, Lang; Stangland, Eric E.; Dumesic, James A.; Mavrikakis, Manos

doi:10.1021/acscatal.1c00940

Hydrodechlorination of 1,2-Dichloroethane on Platinum Catalysts: Insights from Reaction Kinetics Experiments, Density Functional Theory, and Microkinetic Modeling

Journal Article · Tue Jun 15 00:00:00 EDT 2021 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.1c00940· OSTI ID:1835267

^[1]; Stangland, Eric E. ^[2]; ^[3]; ^[3]

Univ. of Wisconsin, Madison, WI (United States); University of Wisconsin-Madison Department of Chemical and Biological Engineering
Dow, Midland, MI (United States)
Univ. of Wisconsin, Madison, WI (United States)

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. Furthermore, our study offers valuable mechanistic insights, which are useful for improving catalysts for this chemistry.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Wisconsin, Madison, WI (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231; FG02-05ER15731

OSTI ID:: 1835267

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 13 Vol. 11; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Hydrodechlorination of 1,2-Dichloroethane on Platinum Catalysts: Insights from Reaction Kinetics Experiments, Density Functional Theory, and Microkinetic Modeling

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