Pt38 as a promising ethanol catalyst: a first principles study

Abstract

This first-principles study predicts Pt₃₈ nanoparticles as a catalyst for ethanol reactions. Starting from the adsorption properties, we shed light on the effectiveness of Pt-based nanoclusters as ethanol catalysts. First, the ethanol adsorption on Pt₃₈ shows that the most stable site positions the molecule with the oxygen anchored on top of an edge, whereas CH₃ is oriented towards the facet and the molecule remains in trans-symmetry. The ethanol–oxygen adsorbed on top of a facet Pt-atom offers the least stable configuration and the longer Pt–O distance (2.318 Å), while the shorter Pt–O distance (2.237 Å) is found when ethanol is on top of an edge site and the molecule is vertically oriented with Gauche symmetry. A shorter Pt–O distance correlates with higher radial breathing of the nanoparticle after ethanol adsorption. Atomic charge redistribution is calculated on all the considered systems and cases. In any event, we show that the Pt-anchor receives a charge, whilst oxygen–ethanol donates electrons. Orbital analysis shows that Pt-anchors and ethanol–oxygen atoms primarily exchange p-charge. Energy barriers associated with the ethanol bond cleavage show that the C–C bond break is slightly more favourable on Pt₃₈ than on an extended Pt(111). In addition, we find that the cleavage of the hydroxyl O–H ethanol bond shows a higher energy barrier while the removal of an H-atom from the CH₃ group is easier. These three facts indicate that the Pt₃₈ nanoparticle enhances ethanol catalysis and hence is a good candidate for ethanol-based fuel cells.