Implicit solvent effects in the determination of Bronsted-Evans-Polanyi relationships for heterogeneously catalyzed reactions
authors Gomes, JRB; Vines, F; Illas, F; Fajin, JLC
nationality International
journal PHYSICAL CHEMISTRY CHEMICAL PHYSICS
keywords GAS SHIFT REACTION; GENERALIZED GRADIENT APPROXIMATION; DENSITY-FUNCTIONAL THEORY; TOTAL-ENERGY CALCULATIONS; WATER DISSOCIATION; SURFACES; DESCRIPTORS; MOLECULES; PD(111); POINTS
abstract Heterogeneously catalyzed reactions take place at the catalyst surface where, depending on the conditions and process, the reacting molecules are either in the 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 influences the atomic structure of the reactants and products as well as the 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 the solute and solvent. The present study shows that the 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 the reactants or products are significantly affected. Encouragingly, the linear equations corresponding to the Bronsted-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 the reaction on the difference surfaces, are similar in the presence or in the absence of the solvent. Despite the associated uncertainties, this suggests that BEP relationships derived without the implicit consideration of the solvent are still valid for predicting the activation energy barriers of catalytic reactions from a reaction descriptor.
publisher ROYAL SOC CHEMISTRY
issn 1463-9076
isbn 1463-9084
year published 2019
volume 21
issue 32
beginning page 17687
ending page 17695
digital object identifier (doi) 10.1039/c9cp02817j
web of science category Chemistry, Physical; Physics, Atomic, Molecular & Chemical
subject category Chemistry; Physics
unique article identifier WOS:000481777100017
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journal analysis (jcr 2019):
journal impact factor 3.43
5 year journal impact factor 3.735
category normalized journal impact factor percentile 69.267
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