The formation of PtRu surface alloys by deposition of submonolayer Pt films on a Ru(0001) substrate and subsequent annealing to about 1350 K and the distribution of the Pt atoms in the surface layer were investigated by scanning tunneling microscopy. Quantitative statistical analysis reveals (i) negligible losses of Pt into subsurface regions up to coverages close below 1 monolayer, (ii) a homogeneous distribution of the Pt atoms over the surface, and (iii) the absence of a distinct long-range or short-range order in the surface layer. In addition, the density of specific adsorption ensembles is analyzed as a function of Pt surface content. Possible conclusions on the process for surface alloy formation are discussed. The results are compared with the properties of PtRu bulk alloys and the findings in previous adsorption studies on similar surface alloys (H. Rauscher, T. Hager, T. Diemant, H. Hoster, F. Bautier de Mongeot and R. J. Behm, Surf. Sci., 2007, 601, 4608; T. Diemant, H Rauscher and R. J. Behm, J. Phys. Chem. C, in press).

The adsorption of hydrogen on structurally well defined PdAu-Pd(111) monolayer surface alloys was investigated in a combined experimental and theoretical study, aiming at a quantitative understanding of the adsorption and desorption properties of individual PdAu nanostructures. Combining the structural information obtained by high resolution scanning tunneling microscopy (STM), in particular on the abundance of specific adsorption ensembles at different Pd surface concentrations, with information on the adsorption properties derived from temperature programmed desorption (TPD) spectroscopy and high resolution electron energy loss spectroscopy (HREELS) provides conclusions on the minimum ensemble size for dissociative adsorption of hydrogen and on the adsorption energies on different sites active for adsorption. Density functional theory (DFT) based calculations give detailed insight into the physical effects underlying the observed adsorption behavior. Consequences of these findings for the understanding of hydrogen adsorption on bimetallic surfaces in general are discussed.

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We report on the structural and electrochemical properties of Au(x)Pt(1-x) surface alloys prepared by Au vapour deposition onto Pt(111) followed by annealing to 1000 K. Driven by configurational entropy, Pt and Au atoms are distributed homogeneously over the surface. On the nm scale, however, atomically resolved scanning tunnelling microscopy images with chemical contrast reveal the formation of nm-sized Pt-rich and Au-rich aggregates, similar to the behaviour recently reported for Pd(x)Ru(1-x)/Ru(0001) [H. Hartmann, T. Diemant, A. Bergbreiter, J. Bansmann, H. E. Hoster, R. J. Behm, Surf. Sci. 2009, 603, 1439]. Based on the STM data, we determine the abundance of specific adsorption sites for different Au contents, and we derive effective pair interaction parameters that allow reproducing the lateral distribution in Monte Carlo simulations. Cyclic voltammograms of the surface alloys have many similarities with Pt(111). H(ad) and OH(ad) related features both decrease with increasing amount of Au. Both seem to adsorb only on Pt sites, but H(ad) requires smaller ensembles of Pt atoms than OH(ad). The onset potential for H(ad)-formation decreases with increasing Au content. This is can be explained by an effect of the Au atoms on the entropy of adsorption.

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The correlation between structural and chemical properties of bimetallic PtRu/Ru(0001) model catalysts and their modification upon stepwise annealing of a submonolayer Pt‐covered Ru(0001) surface up to the formation of an equilibrated PtxRu1−x/Ru(0001) monolayer surface alloy was investigated by scanning tunneling microscopy and by the adsorption of CO and D2 probe molecules. Both temperature‐programmed desorption and IR measurements demonstrate the influence of the surface structure on the adsorption properties of the bimetallic surface, which can be explained by changes of the composition of the adsorption ensembles (ensemble effects) for D adsorption and by changes in the electronic interaction (ligand effects, strain effects) of the metallic constituents for CO and D adsorption upon alloy formation.

The energetics determining the distinct short-range order in two-dimensional (2D) monolayer Cu(x)Pd(1-x) surface alloys on a Ru(0001) substrate were investigated by Monte Carlo simulations and density functional theory calculations. Using a 2D lattice gas Hamiltonian based on effective pair interaction (EPI) parameters, the EPIs were derived for different Cu concentrations with Monte Carlo (MC) simulations by comparing with the atomic distributions obtained from atomic resolution STM images and the related Warren-Cowley short-range order parameters (Hoster et al., Phys. Rev. B, 2006, 73 165413). The ground state structures and mixing energies at 0 K derived from these EPIs agree well with mixing energies determined from DFT calculations of different ordered surface alloys. Additional MC simulations yield rather low transition temperatures which explain the absence of ordered 2D phases in the experiments. The consequences of our findings for the use of alloy surfaces and surface alloys as model systems for adsorption and catalytic reaction studies are discussed.

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