Oxidation of Sn at the Cluster–Support Interface: Sn and Pt–Sn Clusters on TiO₂(110)

The growth of Sn and Pt–Sn clusters on TiO 2 (110) has been studied by scanning tunneling microscopy, X-ray photoelectron spectroscopy (XPS), low energy ion scattering (LEIS), and density functional theory (DFT). At low Sn coverages (0.02 ML), single-layer high clusters of SnO x are formed with a narrow size distribution and uniform spatial distribution. XPS experiments indicate that these clusters consist of oxidized Sn, and the corresponding reduction in the TiO 2 substrate is observed. At higher Sn coverages, the surface is still dominated by two-dimensional clusters of SnO x, but larger three-dimensional clusters of metallic Sn also appear. As the Sn coverage is increased, the number of three-dimensional clusters increases, and the ratio of Sn/SnO x increases, suggesting that SnO x and reduced TiO x form at the cluster–support interface. When Pt is deposited on top of the Sn/SnO x clusters, the relatively mobile Pt atoms diffuse across the TiO 2 surface and become incorporated into existing Sn/SnO x clusters. Furthermore, the addition of Pt to the Sn/SnO x clusters causes the reduction of SnO x to metallic Sn and the oxidation of Ti 3+ to Ti 4+; this behavior is attributed to the formation of Pt–Sn alloy clusters, which results in the diffusion of Sn away from the interface with the TiO 2 support. In contrast, when Sn is deposited on an equal coverage of Pt clusters, new Sn/SnO x clusters are formed that coexist with Pt–Sn clusters. However, the surfaces of both Pt on Sn and Sn on Pt clusters are Sn-rich due to the lower surface free energy of Sn compared to Pt. DFT calculations demonstrate that M–TiO 2 bonding is favored over M–M bonding for M = Sn, unlike for transition metals such as M = Pt, Au, Ni, and Co. Furthermore, the substantial charge transfer from Sn to TiO 2 leads to dipole–dipole repulsion of Sn atoms that prevents agglomeration into the larger clusters that are observed for the mid-late transition metals. DFT studies also confirm that the addition of Pt to a Sn cluster results in strong Pt–Sn bond formation and diminished Sn–O interactions.