Theoretical elucidation of the selectivity changes for the hydrogenation of unsaturated aldehydes on Pt(1 1 1)

On the basis of density functional theory calculations and an original use of a generalized Brönsted–Evans–Polanyi relationship, the key question of the change of selectivity has been solved for hydrogenation of three unsaturated aldehydes (acrolein, crotonaldehyde and prenal) on a Pt(1 1 1) surface. This study supports the idea that the selectivity in favor of the unsaturated alcohol (UOL) is controlled by adsorption thermodynamics of this partially hydrogenated product while the selectivity in favor of the other compound in competition (saturated aldehyde, SAL) obeys a more subtle kinetic control. The present work demonstrates the efficiency and the potentiality of the exposed correlation.