Effect of the presence of tin on inhibition of CO adsorption on Ni4Sn bimetallic clusters

MARIELA FINETTI; GUSTAVO CELIZ; EMILCE E OTTAVIANELLI; ALICIA H JUBERT; REINALDO PIS DIEZ

COMPUTATIONAL MATERIALS SCIENCE

ELSEVIER SCIENCE BV

Lugar: Amsterdam; Año: 2012 vol. 65 p. 494 - 503

0927-0256

The objective of the current study was to determine the role of the tin (Sn) atom in the modification of thecatalytic properties of bimetallic clusters compared with those of pure nickel (Ni) clusters from a theo-retical point of view. Calculations were carried out within the framework of the density functional theory(DFT). Adsorption energies were calculated and orbital, population and energetic analyses were carriedout of the changes due to interaction at all possible sites of the clusters. Orbital analysis of the interactionproved that the mechanism that explains the reported properties shows substantial differences due tothe presence of the Sn atom. The differences are mainly reflected by a large increase in repulsive inter-actions between the occupied orbitals of the adsorbate and those of the bimetallic cluster compared withpure Ni. This increase in repulsions, together with the elimination of sites that involve Sn atoms, causes aglobal decrease in adsorption capacity of CO to the bimetallic cluster, as well as a reduction in adsorptionenergies at certain sites compared with the same site in the pure Ni cluster.