First Principles Calculations for Hydrogenation of Acrolein on Pd and Pt: Chemoselectivity Depends on Steric Effects on the Surface.

Abstract

The chemoselective hydrogenation of acrolein on Pt(111) and Pd(111) surfaces is investigated employing density functional theory calculations. The computed potential energy surfaces together with the analysis of reaction mechanisms demonstrate that steric effects are an important factor that governs chemoselectivity. The reactions at the C=O functionality require more space than the reactions at the C=C functionality. Therefore the formation of allyl alcohol is more favorable at low coverage, while the reduction of the C=C bond and the formation of propanal becomes kinetically more favorable at higher coverage. The elementary reaction steps are found to follow different reaction mechanisms, which are identified according to terminology typically used in organometallic catalysis. The transition state scaling (TSS) relationship is demonstrated and the origin of multiple TSS lines is linked to variation of an internal electronic structure of a carbon skeleton.