We report on the structure and electrochemical adsorption properties of well-defined pseudomorphic Pt mono- and multilayers on Ru(0001). These act as model surfaces for Pt(111) with slightly decreased affinity to adsorbed hydrogen (H(ad)) and hydroxyl (OH(ad)). In cyclic voltammograms, this is reflected in more negative/positive potential regions for the reversible adsorption of upd-H(ad)/OH(ad), respectively, compared to Pt(111). For upd-H(ad), we show that the corresponding trends can be predicted with high accuracy by density functional theory (DFT). In particular, the upd-H(ad) onset regions can be precisely simulated using the H(ad) adsorption energies from DFT, the layer thickness distribution from STM, and the base voltammogram of Pt(111) as reference.

The competition between intermolecular interactions and lateral variations in the molecule-substrate interactions has been studied by scanning tunneling microscopy (STM), comparing the phase formation of (sub)monolayers of the organic molecule 2,4'-BTP on buckled graphene/Ru(0001) and Ag(111) oriented thin films on Ru(0001). On the Ag films, the molecules form a densely packed 2D structure, while on graphene/Ru(0001), only the areas between the maxima are populated. The findings are rationalized by a high corrugation in the adsorption potential for 2,4'-BTP molecules on graphene/Ru(0001). These findings are supported by temperature programmed desorption (TPD) experiments and theoretical results.

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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