Mechanism of Trichloroethene Hydrodehalogenation: A First-Principles Kinetic Monte Carlo Study
| Autor: | Karoliina Honkala, Anna Kausamo, Jenni Andersin |
|---|---|
| Rok vydání: | 2014 |
| Předmět: |
chemistry.chemical_classification
Reaction mechanism Work (thermodynamics) Chemistry Kinetic energy Surfaces Coatings and Films Electronic Optical and Magnetic Materials Catalysis General Energy Adsorption Hydrocarbon Mechanism (philosophy) Computational chemistry Organic chemistry Kinetic Monte Carlo Physical and Theoretical Chemistry ta116 |
| Zdroj: | The Journal of Physical Chemistry C. 118:19759-19767 |
| ISSN: | 1932-7455 1932-7447 |
| DOI: | 10.1021/jp503494g |
| Popis: | A hydrodehalogenation (HDC) reaction of trichloroethene (TCE) has gained a lot of interest due to its possible application in water purification, but the reaction mechanism has been subject to much controversy. In this work, HDC of TCE on Pd(111) was examined by carrying out kinetic Monte Carlo simulations based on DFT-calculated thermodynamic and kinetic parameters. Obtained kMC results show that the HDC follows a so-called direct pathway, which means that, after adsorption on a catalyst, TCE quickly dechlorinates, producing CH–C and then, more slowly, hydrogenates to form hydrocarbon products. This is reflected in the surface coverage snapshots, where intermediates corresponding to the direct pathway are mostly seen. We also investigated the effect of lateral Cl–Cl repulsions on the distribution and coverage of intermediates, and on the reaction mechanism. In general, the adsorbed Cl atoms retard further dechlorinations, leading to less effective HDC, which is in line with experimental observations. |
| Databáze: | OpenAIRE |
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