Adsorption and ring-opening of lactide on the chiral metal surface Pt(321)S studied by density functional theory
Journal Publication ResearchOnline@JCUAbstract
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.
Journal
Journal of Chemical Physics
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Volume
142
ISBN/ISSN
1089-7690
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Issue
4
Pages Count
7
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Publisher
American Institute of Physics
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DOI
10.1063/1.4906151