Implicit solvent effects in the determination of Bronsted-Evans-Polanyi relationships for heterogeneously catalyzed reactions

Heterogeneous catalyzed reactions take place at the catalyst surface where, depending on the conditions and process, the reacting molecules are either in gas or liquid phase. In the latter case, computational heterogeneous catalysis studies usually neglect solvent effects. In this work, we systemati...

Descripción completa

Detalles Bibliográficos
Autores: Gomes, José R. B., Viñes Solana, Francesc, Illas i Riera, Francesc, Fajin, Jose L. C.
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2019
País:España
Institución:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:2445/165639
Acceso en línea:https://hdl.handle.net/2445/165639
Access Level:acceso abierto
Palabra clave:Catàlisi heterogènia
Dissolvents
Metalls de transició
Heterogeneus catalysis
Solvents
Transition metals
Descripción
Sumario:Heterogeneous catalyzed reactions take place at the catalyst surface where, depending on the conditions and process, the reacting molecules are either in gas or liquid phase. In the latter case, computational heterogeneous catalysis studies usually neglect solvent effects. In this work, we systematically analyze how the electrostatic contribution to solvent effects influence the atomic structure of reactants and products as well as adsorption, activation and reaction energy for the dissociation of water on several planar and stepped transition metal surfaces. The solvent effects were accounted for through an implicit model that describes the effect of electrostatics, cavitation, and dispersion on the interaction between solute and solvent. The present study shows that activation energy barriers are only slightly influenced by the inclusion of the electrostatic solvent effects accounted for in a continuum solvent approach whereas the adsorption energies of reactants or products are significantly affected. Encouragingly, the linear equations corresponding to the Brønsted-Evans-Polanyi relationships (BEPs) relating the activation energies for the dissociation reaction with a suitable descriptor, e.g. the adsorption energies of the products of reaction on the difference surfaces, are similar in the presence or in the absence of the solvent. This suggests that BEP relationships derived without the implicit consideration of the solvent are still valid for predicting activation energy barriers of catalytic reactions from a reaction descriptor.