Ethanol chemisorption on core-shell Pt-nanoparticles: an ab-initio study

TL;DR

This study uses ab-initio calculations to analyze ethanol chemisorption on core-shell Pt-based nanoalloys, revealing how nanoparticle distortion and electron transfer influence binding energy and identifying Pd@Pt as a promising catalyst.

Contribution

It provides a detailed ab-initio analysis of ethanol adsorption on Pt-based nanoalloys, highlighting the role of nanoparticle distortion and core-dependent electron transfer in chemisorption.

Findings

Ethanol binding energy increases on nanoparticles compared to nanofilms.

Nanoparticle distortion affects ethanol adsorption and is site-dependent.

Pd@Pt nanoalloys show the most promising features for ethanol oxidation.

Abstract

By means of ab-initio calculations, we have investigated the chemisorption paroperties of ethanol onto segregating binary nanoalloys. We select nanostructures with icosahedral shape of 55 atoms with a Pt outermost layer over a M core with M=Ag,Pd,Ni. With respect to nanofilms with equivalent composition, there is an increse of the ethanol binding energy. This is not merely due to observed shortening of the Pt-O distance but depends on the nanoparticle distortion after ethanol adsorption. This geometrical distortion within the nanoparticle can be interpreted as a radial breathing, which is sensitive to the adsortion site, identified by the O-anchor point and the relative positions of the ethyl group. More interestingly, being core-dependent -larger in Pd@Pt and smaller in Ni@Pt-, it relates to an effective electron transfer from ethanol and the M-core towards the Pt-shell. On the view of this new analysis, Pd@Pt nanoalloys show the most promissing features for ethanol oxidation.