Adsorption and ring-opening of lactide on the chiral metal surface Pt(321)S studied by density functional theory

Franke, J-F., and Kosov, D.S. (2015) Adsorption and ring-opening of lactide on the chiral metal surface Pt(321)S studied by density functional theory. Journal of Chemical Physics, 142 (4). pp. 1-7.

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Abstract

We study the adsorption and ring-opening of lactide on the naturally chiral metal surface Pt(321) S . Lactide is a precursor for polylactic acid ring-opening polymerization, and Pt is a well known catalyst surface. We study, here, the energetics of the ring-opening of lactide on a surface that has a high density of kink atoms. These sites are expected to be present on a realistic Pt surface and show enhanced catalytic activity. The use of a naturally chiral surface also enables us to study potential chiral selectivity effects of the reaction at the same time. Using density functional theory with a functional that includes the van der Waals forces in a first-principles manner, we find modest adsorption energies of around 1.4 eV for the pristine molecule and different ring-opened states. The energy barrier to be overcome in the ring-opening reaction is found to be very small at 0.32 eV and 0.30 eV for LL- and its chiral partner DD-lactide, respectively. These energies are much smaller than the activation energy for a dehydrogenation reaction of 0.78 eV. Our results thus indicate that (a) ring-opening reactions of lactide on Pt(321) can be expected already at very low temperatures, and Pt might be a very effective catalyst for this reaction; (b) the ring-opening reaction rate shows noticeable enantioselectivity.

Item ID: 38519
Item Type: Article (Refereed Research - C1)
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Copyright 2015 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics.

The following article appeared in Franke, J-F., and Kosov, D.S. (2015) Adsorption and ring-opening of lactide on the chiral metal surface Pt(321)S studied by density functional theory. Journal of Chemical Physics, 142 (4). pp. 1-7. and may be found at http://dx.doi.org/10.1063/1.4906151.

ISSN: 1089-7690
Funders: Francqui Foundation, and Programme d’Actions de Recherche Concertées de la Communauté Francaise, Belgium, Fonds de la Recherche Scientifique de Belgique (F.R.S.-FNRS)
Projects and Grants: F.R.S.-FNRS Grant No. 2.5020.11
Date Deposited: 23 Jun 2015 23:47
FoR Codes: 03 CHEMICAL SCIENCES > 0307 Theoretical and Computational Chemistry > 030701 Quantum Chemistry @ 100%
SEO Codes: 97 EXPANDING KNOWLEDGE > 970103 Expanding Knowledge in the Chemical Sciences @ 100%
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