Au, Pt, and Au−Pt clusters were grown on TiO2(110) at room temperature and studied by scanning tunneling
microscopy. For the same metal coverages, the deposition of pure Pt produces smaller clusters and higher
cluster densities compared to pure Au because of the greater mobility of Au on the surface. Heating the
surface causes greater sintering of the Au clusters compared to Pt; this behavior is explained by the stronger
metal−metal bonds for Pt and the fact that atom detachment is the rate-limiting step in cluster sintering. For
the deposition of 0.024 ML of Pt followed by 0.072 ML of Au, bimetallic clusters are formed from the
nucleation of Au at existing Pt clusters, whereas the reverse order of deposition results in pure Pt clusters and
pure Au clusters coexisting on the surface. The presence of Pt in the bimetallic Pt−Au clusters inhibits sintering,
and the average size of the clusters after annealing decreases with increasing Pt composition. Low energy ion
scattering experiments demonstrate that the deposition of Au on Pt does not produce core−shell structures
with Au on top. Bulk thermodynamics predicts that the cluster surfaces should be pure Au, given that the Au
surface free energy is lower than that of Pt, and Au and Pt are immiscible at the compositions studied here.
However, surface compositions of the Au−Pt clusters are 10−30% richer in Pt compared to the overall
compositions for total coverages of 0.10 ML and 25−75% Pt. These results demonstrate that Au and Pt
atoms can intermix at room temperature and the surface properties of Au−Pt nanoclusters are different from
those of the bulk. Grazing angle X-ray photoelectron spectroscopy experiments show that annealed Au−Pt
clusters are covered by reduced titania. Annealing the Au−Pt clusters to temperatures above 600 K induces
encapsulation of the clusters, but the presence of Au at the cluster surface decreases the extent of encapsulation
compared to that of pure Pt clusters.
Combining the results from experimental (STM and IRAS) and theoretical (DFT) studies of water adsorption on gold, we show that the Au(111) surface is hydrophobic. The weak interaction of water with Au induces the formation of a unique double bilayer, which itself is hydrophobic due to the internal locking of all hydrogen bonds within the bilayer and between the two bilayers of the water clusters.
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