Metal–support interaction effects on chemo–regioselectivity: Hydrogenation of crotonaldehyde on Pt13/CeO2(1 1 1)

• We perform DFT + U calculations for crotonaldehyde adsorption on Pt13/CeO2(1 1 1).
• Its selective hydrogenation is explored at different active sites.
• The hydrogenation activation barriers are large and leveled compared to Pt(1 1 1).
• One exception is found for the active site at the interface.
• The selectivity is globally controlled by the desorption steps of the products.

The metal–support interaction on the chemical reactivity is illustrated here by density functional theory calculations for the hydrogenation of crotonaldehyde on Pt13 clusters deposited on CeO2(1 1 1). Adsorption of crotonaldehyde on the supported cluster is globally strengthened, compared to Pt(1 1 1), both on top of the cluster and at the interface with ceria. The activation barriers of the first and the second hydrogenation steps at both CC and CO bonds are consequently increased, but particularly at CO on top of the cluster, with respect to Pt(1 1 1). In contrast, the hydrogenation at CO is far easier at the interface with ceria, which underlines the key role of the support. The considered model shows a preferential route toward the formation of the saturated aldehyde, in contrast to the measurements. This study paves the way to advanced theoretical models with larger nanoparticles supported on reduced ceria in realistic conditions of environment.

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