Mechanistic Study of 1,2-Dichloroethane Hydrodechlorination on Cu-Rich Pt–Cu Alloys: Combining Reaction Kinetics Experiments with DFT Calculations and Microkinetic Modeling

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

doi:10.1021/acssuschemeng.1c06899

Title: Mechanistic Study of 1,2-Dichloroethane Hydrodechlorination on Cu-Rich Pt–Cu Alloys: Combining Reaction Kinetics Experiments with DFT Calculations and Microkinetic Modeling

Journal Article · 18 January 2022 · ACS Sustainable Chemistry & Engineering

DOI: https://doi.org/10.1021/acssuschemeng.1c06899 · OSTI ID:1876045

^[1]; Stangland, Eric ^[2];

^[3];

^[3]

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

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.

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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:: 1876045

Journal Information:: ACS Sustainable Chemistry & Engineering, Journal Name: ACS Sustainable Chemistry & Engineering Journal Issue: 4 Vol. 10; ISSN 2168-0485

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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1
2-Dichloroethane
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Adsorption
Alloys
Catalysts
Density functional theory
Hydrocarbons
Hydrodechlorination
Microkinetic model
Platinum
Platinum−copper alloy
Reaction mechanism

Title: Mechanistic Study of 1,2-Dichloroethane Hydrodechlorination on Cu-Rich Pt–Cu Alloys: Combining Reaction Kinetics Experiments with DFT Calculations and Microkinetic Modeling

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