4.6 Article

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

期刊

ACS SUSTAINABLE CHEMISTRY & ENGINEERING
卷 10, 期 4, 页码 1509-1523

出版社

AMER CHEMICAL SOC
DOI: 10.1021/acssuschemeng.1c06899

关键词

1,2-Dichloroethane; Hydrodechlorination; Platinum-copper alloy; Reaction mechanism; Density functional theory; Microkinetic model

资金

  1. Dow University Partner Initiative
  2. UW-Madison, under Dow agreement [235744C]
  3. DOE-BES, Division of Chemical Sciences, Catalysis Science Program [DE-FG02-05ER15731]
  4. U.S. Department of Energy, Office of Science [DE-AC02-05CH11231]
  5. UW-Madison Center for High Throughput Computing (CHTC)
  6. Wisconsin Alumni Research Foundation
  7. Wisconsin Institute for Discovery
  8. National Science Foundation

向作者/读者索取更多资源

Cu-rich Pt-Cu bimetallic catalysts were studied for the hydrodechlorination of 1,2-dichloroethane. Experimental and computational results showed that increasing Cu content destabilizes C-2-species adsorption while stabilizing atomic chlorine binding. A microkinetic model based on DFT calculations was constructed and confirmed by experiments, providing insights into the reaction mechanism and active sites.
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 C-2-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. 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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