Tuning catalytic reactivity on metal surfaces: Insights from DFT

•DFT shows how the environment of the active sites can tune the catalytic reactivity.•Alloying Pt with Sn (or Pd with Au) weakens butene adsorption and increases selectivity for butadiene partial hydrogenation.•On PtSn, the non-selective pathway for butadiene hydrogenation through a metallacycle intermediate is disadvantaged.•For alcohol dehydrogenation, co-adsorbed water plays a key role in assisting OH bond breaking.

Density Functional Theory (DFT) calculations show on two examples how catalytic reactivity qualitatively depends on the environment of the active sites. The example of butadiene selective hydrogenation to butenes on Pt or Pd first illustrates how alloying this catalytically active metal with a non- or less reactive elements (Sn or Au, respectively) allows weaker catalyst–molecule interactions and favors the desorption of butenes. It also shows that, from this weakening of the interactions, new reaction pathways are opened and non-selective pathways through a metallacycle intermediate are disadvantaged. Both effects concur on PtSn for an improved selectivity in butenes, while on the PdAu alloy, the gain in selectivity is explained mainly by the easier butene desorption. The dehydrogenation of ethanol on Rh and Pt surfaces shows how co-adsorbates, as water solvent molecules, can interfere with the catalytic elementary steps, assisting OH bond breaking and disadvantaging CH dissociation. The balance between these two effects is metal dependent. Ethanol interacts by a strong H-bond with the H2O pre-covered surface, in a more stabilizing way than for the simple adsorption on the bare metal. The surface H2O (or surface-OH) complex can hence be seen as the true active site for the reaction. It is hence important to include the influence of the environment, from the surface part or from the reactant part, for an accurate modeling of heterogeneous catalytic reactions.

Graphical abstractDFT calculations show that the environment of the active sites (left : water co-adsorbate, right metallic alloy) allow tuning catalytic activity and selectivityFigure optionsDownload full-size imageDownload high-quality image (165 K)Download as PowerPoint slide