Mechanistic Study of 1,2-Dichloroethane Hydrodechlorination on Cu-Rich Pt–Cu Alloys: Combining Reaction Kinetics Experiments with DFT Calculations and Microkinetic Modeling
Abstract
Cu-rich Pt–Cu bimetallic catalysts are among the most promising candidates for actively catalyzing the hydrodechlorination of 1,2-dichloroethane (1,2-DCA) toward ethylene production. Combining reaction kinetics experiments with density functional theory (DFT) calculations and mean-field microkinetic modeling, we present a systematic mechanistic study for 1,2-DCA hydrodechlorination on Cu-rich Pt–Cu alloy catalysts. Our DFT (PBE+(TS+SCS)) results suggest that increasing Cu content in the Pt–Cu alloy destabilizes C2-species adsorption while stabilizing the binding of atomic chlorine. The reaction energetics of all the elementary steps in the 1,2-DCA reaction network were calculated on a Pt1Cu3(111) model surface. The DFT results were then used to construct a microkinetic model, and the model-predicted reaction rates were compared with our reaction kinetics experimental results on a Cu-rich SiO2-supported Pt–Cu alloy catalyst through a parameter estimation procedure. Both the reaction kinetics experiments and the microkinetic model after parameter adjustments yielded 100% selectivity to ethylene. The microkinetic model pointed to a reaction pathway involving two sequential chlorine-removal steps on the Pt–Cu alloy catalyst, a mechanism distinct from the one previously identified on pure Pt/SiO2 catalysts, which involved an initial hydrogen-removal step. Adjustments to the DFT-derived parameters indicate the possible formation of chlorine-induced Cu-enriched surface sites during 1,2-DCA hydrodechlorination conditions, sitesmore »
- 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:
- 1876045
- Grant/Contract Number:
- FG02-05ER15731; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Sustainable Chemistry & Engineering
- Additional Journal Information:
- Journal Volume: 10; Journal Issue: 4; Journal ID: ISSN 2168-0485
- 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−copper alloy; Reaction mechanism; Density functional theory; Microkinetic model; Adsorption; Alloys; Catalysts; Hydrocarbons; Platinum
Citation Formats
Xu, Lang, Stangland, Eric, Dumesic, James A., and Mavrikakis, Manos. Mechanistic Study of 1,2-Dichloroethane Hydrodechlorination on Cu-Rich Pt–Cu Alloys: Combining Reaction Kinetics Experiments with DFT Calculations and Microkinetic Modeling. United States: N. p., 2022.
Web. doi:10.1021/acssuschemeng.1c06899.
Xu, Lang, Stangland, Eric, Dumesic, James A., & Mavrikakis, Manos. Mechanistic Study of 1,2-Dichloroethane Hydrodechlorination on Cu-Rich Pt–Cu Alloys: Combining Reaction Kinetics Experiments with DFT Calculations and Microkinetic Modeling. United States. https://doi.org/10.1021/acssuschemeng.1c06899
Xu, Lang, Stangland, Eric, Dumesic, James A., and Mavrikakis, Manos. Wed .
"Mechanistic Study of 1,2-Dichloroethane Hydrodechlorination on Cu-Rich Pt–Cu Alloys: Combining Reaction Kinetics Experiments with DFT Calculations and Microkinetic Modeling". United States. https://doi.org/10.1021/acssuschemeng.1c06899. https://www.osti.gov/servlets/purl/1876045.
@article{osti_1876045,
title = {Mechanistic Study of 1,2-Dichloroethane Hydrodechlorination on Cu-Rich Pt–Cu Alloys: Combining Reaction Kinetics Experiments with DFT Calculations and Microkinetic Modeling},
author = {Xu, Lang and Stangland, Eric and Dumesic, James A. and Mavrikakis, Manos},
abstractNote = {Cu-rich Pt–Cu bimetallic catalysts are among the most promising candidates for actively catalyzing the hydrodechlorination of 1,2-dichloroethane (1,2-DCA) toward ethylene production. Combining reaction kinetics experiments with density functional theory (DFT) calculations and mean-field microkinetic modeling, we present a systematic mechanistic study for 1,2-DCA hydrodechlorination on Cu-rich Pt–Cu alloy catalysts. Our DFT (PBE+(TS+SCS)) results suggest that increasing Cu content in the Pt–Cu alloy destabilizes C2-species adsorption while stabilizing the binding of atomic chlorine. The reaction energetics of all the elementary steps in the 1,2-DCA reaction network were calculated on a Pt1Cu3(111) model surface. The DFT results were then used to construct a microkinetic model, and the model-predicted reaction rates were compared with our reaction kinetics experimental results on a Cu-rich SiO2-supported Pt–Cu alloy catalyst through a parameter estimation procedure. Both the reaction kinetics experiments and the microkinetic model after parameter adjustments yielded 100% selectivity to ethylene. The microkinetic model pointed to a reaction pathway involving two sequential chlorine-removal steps on the Pt–Cu alloy catalyst, a mechanism distinct from the one previously identified on pure Pt/SiO2 catalysts, which involved an initial hydrogen-removal step. Adjustments to the DFT-derived parameters indicate the possible formation of chlorine-induced Cu-enriched surface sites during 1,2-DCA hydrodechlorination conditions, sites that are more active than those encountered in the bulk Pt1Cu3(111) alloy surface. Furthermore, our study offers valuable initial insights on the 1,2-DCA hydrodechlorination reaction mechanism and the nature of the active sites on PtCu bimetallic catalysts.},
doi = {10.1021/acssuschemeng.1c06899},
journal = {ACS Sustainable Chemistry & Engineering},
number = 4,
volume = 10,
place = {United States},
year = {Wed Jan 19 00:00:00 EST 2022},
month = {Wed Jan 19 00:00:00 EST 2022}
}
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