Density Functional Theory Analysis of Dichloromethane andHydrogen Interaction with Pd Clusters: First Step toSimulate Catalytic Hydrodechlorination
Entity
UAM. Departamento de Química Física AplicadaPublisher
American Chemical SocietyDate
2011-06-30Citation
The Journal of Physical Chemistry C 115.29 (2011): 14180-14192ISSN
1932-7447 (print); 1932-7455 (online)Funded by
We are grateful to the Spanish “Ministerio de Ciencia e Innovacion”and“Comunidad de Madrid ”for financial support (CTQ2008-04751, CTQ2008-05641, and S2009/PPQ-1545). We are also very grateful to “Centro de Computacion Científica de la Universidad Aut onoma de Madrid” for computational facilitiesProject
Gobierno de España. CTQ2008-04751; Gobierno de España. CTQ2008-05641; Comunidad de Madrid. S2009/PPQ-1545Editor's Version
https://doi.org/10.1021/jp200329jSubjects
Adsorption; catalysts; cluster chemistry; palladium; quantum mechanics; Física; QuímicaRights
© American Chemical SocietyAbstract
A density functional theory (DFT) analysis hasbeen conducted for the gas-phase hydrodechlorination (HDC) ofdichloromethane (DCM) with palladium catalyst to achieve abetter knowledge of the reaction mechanism involved in the HDCprocess, which constitutes an emerging technology for the treat-ment of organochlorinated contaminants. The computationalstudy included the effect of size, oxidation state, and spin config-uration of Pd cluster on the adsorption of H2and DCM reactantson the catalyst surface. Calculations described the activation of H2by Pd clusters through a dissociative adsorption with low enthalpy values. In addition, partially and fully dissociated DCMintermediates on Pd surface were predicted by DFT calculations. Remarkably, the dissociative adsorption of DCM on Pd active sitesoccurs via the scission of C Cl bonds, promoted by the formation of C Pd linkages, implying high adsorption enthalpy. Thecomputational results showed that DCM can be also molecularly adsorbed on both zerovalent and electrodeficient Pd species.However, the nondissociative adsorption of DCM over electrodeficient Pd cluster is remarkably favored in energy, with adsorptionenthalpies (∼ 50 kcal/mol) corresponding to chemisorption. Current theoretical evidence explained the deactivation of Pd/ACcatalyst as a consequence of the selective poisoning of electrodeficient Pd active centers by chlorinated hydrocarbons, in goodagreement with our previous experimental findings
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Google Scholar:Omar, Salama
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Palomar Herrero, José Francisco
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Gómez Sainero, Luisa María
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Álvarez Montero, Ariadna
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Martín Martínez, María
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Rodríguez Jiménez, Juan José
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