Entropy Effects in Atom Distribution and Electrochemical Properties of AuxPt1-x/Pt(111) Surface Alloys

We report on the structural and electrochemical properties of AuxPt1-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 PdxRu1-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 OHad 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 OHad. 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.