Developing powerful next-generation technologies for catalysis, energy conversion, and energy storage relies on understanding and controlling molecular transformations at complex interfaces. However, relatively little is known about the fundamental molecular-scale phenomena driving chemical selectivity at functional and complex interfaces. Our work aims to investigate mechanisms of enantioselectivity in heterogeneous catalysis. Specifically, by investigating hydrogenation reactions of both the (R)- and (S)- enantiomers of limonene on the chiral Pt(532) surface, we will provide insight into the adsorbate-surface interactions that lead to enantiomeric excess in the formation of the chiral product, menthene. Here, we report our initial results of this work, which uses computational methods to probe molecular adsorption of limonene followed by catalytic hydrogenation. Our approach utilizing density functional theory and molecular dynamics combined with the results of recent experimental sum-frequency generation experiments, reveals likely adsorption orientations and reaction pathways of both enantiomers on the Pt(532) surface. A comparison of adsorption and reaction mechanisms across both enantiomers leads to a fundamental description of the atomic-scale interactions that produce enantioselectivity in adsorption and reactions of limonene on a chiral platinum surface. We hope that these results provide qualitative insight into how enantioselectivity is achieved in heterogeneous catalysis at intrinsically chiral metal surfaces.

Chiral selectivity in heterogeneous catalysis

256th National Meeting (2018)

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