Characterizing the surface compositions of supported bimetallic PtSn clusters: Effects of cluster-support interactions and surface adsorbates

PtSn bimetallic clusters on TiO₂(110) and highly oriented pyrolytic graphite (HOPG) surfaces have been characterized by scanning tunneling microscopy, low energy ion scattering (LEIS), X-ray photoelectron spectroscopy, and temperature programmed desorption (TPD); density functional theory (DFT) calculations have also been performed to better understand adsorption of CO and D₂ on the PtSn surfaces. On TiO₂ at coverages of 2 ML of Pt and 2 ML of Sn, exclusively bimetallic clusters are formed for both orders of deposition because clusters of the first metal completely cover the surface such that all atoms of the second metal are incorporated into the existing clusters. In contrast, on HOPG, the high mobility and weak cluster-support interactions on HOPG result in much larger 2 ML monometallic clusters (∼30 Å high) that do not completely cover the surface, and deposition of the second metal produces larger clusters as well as smaller ones. Despite the difference in cluster morphologies for the different orders of deposition and supports, the LEIS experiments demonstrate that in all cases, the PtSn clusters are rich in Sn at the surface, as expected based on the lower surface free energy for Sn compared to Pt. Furthermore, the +0.2 eV shift in the Sn(3d_5/2) binding energy observed on all surfaces in the presence of Pt is consistent with PtSn alloy formation. Deposition of 2 ML of Sn on TiO₂ produces two-dimensional clusters with oxidation of Sn and reduction of titania at the cluster-support interface, but addition of Pt to the Sn clusters causes Sn to diffuse away from this interface, leaving Sn in the metallic state. TPD experiments on 2 ML Pt/TiO₂ with increasing coverages of Sn show that the number of adsorption sites for D₂ sharply decreases to nearly zero at 0.5 ML, while CO adsorption decreases to zero only at much higher Sn coverages of 2 ML. DFT studies for Sn modified Pt surfaces and bulk structures demonstrate that for CO adsorption at low Sn coverages (≤0.25 ML), the strong Pt-CO interactions induce diffusion of Pt to the cluster surface and the formation of a bulk Pt₃Sn alloy, whereas D₂ adsorption does not lead to interactions with the Pt surface that are strong enough to induce alloy formation. A single Sn adatom prevents D₂ adsorption on four neighboring Pt atoms via site-blocking and the donation of electron density to Pt.