Hydrodechlorination of 1,2-Dichloroethane on Platinum Catalysts: Insights from Reaction Kinetics Experiments, Density Functional Theory, and Microkinetic Modeling
Abstract
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 usefulmore »
- Authors:
-
[1];
[1];
[1]
- Univ. of Wisconsin, Madison, WI (United States)
- Dow, Midland, MI (United States)
- Publication Date:
- Research Org.:
- Univ. of Wisconsin, Madison, WI (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1835267
- Grant/Contract Number:
- FG02-05ER15731; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Catalysis
- Additional Journal Information:
- Journal Volume: 11; Journal Issue: 13; Journal ID: ISSN 2155-5435
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 1,2-dichloroethane; hydrodechlorination; platinum catalyst; reaction kinetic; reaction mechanism; density functional theory; microkinetic model
Citation Formats
Xu, Lang, Stangland, Eric E., Dumesic, James A., and Mavrikakis, Manos. Hydrodechlorination of 1,2-Dichloroethane on Platinum Catalysts: Insights from Reaction Kinetics Experiments, Density Functional Theory, and Microkinetic Modeling. United States: N. p., 2021.
Web. doi:10.1021/acscatal.1c00940.
Xu, Lang, Stangland, Eric E., Dumesic, James A., & Mavrikakis, Manos. Hydrodechlorination of 1,2-Dichloroethane on Platinum Catalysts: Insights from Reaction Kinetics Experiments, Density Functional Theory, and Microkinetic Modeling. United States. https://doi.org/10.1021/acscatal.1c00940
Xu, Lang, Stangland, Eric E., Dumesic, James A., and Mavrikakis, Manos. Tue .
"Hydrodechlorination of 1,2-Dichloroethane on Platinum Catalysts: Insights from Reaction Kinetics Experiments, Density Functional Theory, and Microkinetic Modeling". United States. https://doi.org/10.1021/acscatal.1c00940. https://www.osti.gov/servlets/purl/1835267.
@article{osti_1835267,
title = {Hydrodechlorination of 1,2-Dichloroethane on Platinum Catalysts: Insights from Reaction Kinetics Experiments, Density Functional Theory, and Microkinetic Modeling},
author = {Xu, Lang and Stangland, Eric E. and Dumesic, James A. and Mavrikakis, Manos},
abstractNote = {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.},
doi = {10.1021/acscatal.1c00940},
journal = {ACS Catalysis},
number = 13,
volume = 11,
place = {United States},
year = {Tue Jun 15 00:00:00 EDT 2021},
month = {Tue Jun 15 00:00:00 EDT 2021}
}
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