Abstract
We have studied the local properties of single Pt atoms adsorbed on hydroxylated ${\mathrm{TiO}}_{2}(110)$-($1\ifmmode\times\else\texttimes\fi{}1$) by combining noncontact atomic force microscopy (nc-AFM) and first-principles calculations. Room-temperature high-resolution nc-AFM images for the most frequently observed contrast modes reveal bright and elongated protrusions that can be traced back to the Pt atoms, and that are centered on the fivefold coordinated titanium rows, confined between two bridging oxygen rows. These observations are in line with the theoretical results, as the lowest energy sites for the Pt atom on the ${\mathrm{TiO}}_{2}(110)$ surface are in the neighborhood of the titanium rows, and high energy barriers have to be overcome to displace the Pt atom over the bridging oxygen rows. Single Pt atoms can be distinguished from H adsorbates (OH defects) due to their characteristic shape and binding site and, because they appear as the brightest surface features in all of the contrast modes. Force spectroscopy data over the protrusion and hole imaging modes and the corresponding tip-sample forces, simulated with O and OH terminated ${\mathrm{TiO}}_{2}$ nanoclusters, provide an explanation for this puzzling result in terms of the intrinsic strength of the interaction with the Pt adatom and the adatom and tip apex relaxations induced by the tip-sample interaction. These imaging mechanisms can be extended to other electropositive metal dopants and support the use of nc-AFM not only to characterize their adsorption structure but also to directly probe their chemical reactivity.
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