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

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.

Automated summary

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.