Effects of chemisorption of electron acceptor elements on the stability of platinum clusters

The extended Hückel method (EHM) is used here to investigate how the bond strengths of Pt(100) and Pt(111) clusters, containing 9 and 10 atoms, respectively, are affected by the chemisorbed H, O, Cl, or S atoms. Three adsorption sites are considered on each cluster. For most adsorption sites Cl and S weaken all the PtPt bonds, while H and O strengthen the bonds between some Pt atoms and weaken the bonds between some other Pt atoms. The enhanced mobility of the Pt atoms, that occurs upon adsorption of the above elements, is proposed as the mechanism behind the first step in corrosive chemisorption and in the redispersion of supported Pt catalysts. The strong destabilizing effect of S and Cl is attributed to the empty d orbitais of these elements. An attempt is made to explain the poisoning by Sulfur on the basis of long range structural and electronic changes that occur in the Pt clusters upon chemisorption of S.