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Article Dans Une Revue Physical Chemistry Chemical Physics Année : 2019

Can microsolvation effects be estimated from vacuum computations? A case-study of alcohol decomposition at the H 2 O/Pt(111) interface

Résumé

Converting biomass into sustainable chemicals and energy feedstocks requires innovative heterogeneous catalysts able to efficiently work in aqueous conditions. Computational chemistry is a key asset in the design of these novel catalysts, but it has to face two challenges: the large reaction networks and the potential role of hydration. They can be addressed using scaling relations such as Brønsted-Evans-Polanyi (BEP) and solvation models, respectively. In this study, we show that typical reaction and activation energies of alcohol decomposition on Pt(111) are not strongly modified by the inclusion of the water solvent as a continuum model. In contrast, adding a single water molecule strongly favors O-H and C-OH scission while it prevents CO and to a lesser extent CC scissions. The resulting BEP relationships partially reflect these changes induced by the solvent. Predicting Pt-catalyzed alcohol decomposition in water thus should account for the influence of the solvent on thermodynamics and kinetics. In addition, we found that the reaction energy obtained in presence of an explicit water molecule scales with the ones obtained in vacuum. Hence, we reveal that vacuum computations in combination with corrections based on our linear regressions are able to capture the important H-bonding effect.
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Dates et versions

hal-02077898 , version 1 (24-03-2019)

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Benjamin Schweitzer, Stephan N. Steinmann, Carine Michel. Can microsolvation effects be estimated from vacuum computations? A case-study of alcohol decomposition at the H 2 O/Pt(111) interface. Physical Chemistry Chemical Physics, 2019, 21 (10), pp.5368-5377. ⟨10.1039/C8CP06331A⟩. ⟨hal-02077898⟩
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