Electrical and structural properties of stepped, partially reconstructed Au(11n) surfaces in HClO4 and H2SO4 electrolytes

We have studied the interface capacitance and the voltammograms of Au(11n) (n=5,7, 11, 17) and of Au (100) electrodes in 5 mM HClO4 and 5 mM H2SO4 after immersion into the electrolyte solution at -0.4 V versus a saturated calomel electrode. The minima of the capacitance curves measured in positive sweeps continuously shift towards positive potentials as function of 1/n. All voltammograms, even that of Au(1 1 5), display peaks that are characteristic for lifting of surface reconstructions, albeit at different potentials. Thus, all vicinal surfaces appear to have at least sections that allow reconstruction. This inference is consistent with STM-profiles of an Au(1 1 9) surface which displays a wide range of local inclination angles corresponding to local (11n)-orientations with 3.5 < n < infinity. A numerical analysis of the voltammograms shows the existence of three different ranges of transition potentials for the lifting of the reconstruction. The transition potentials are assigned to three different structures of the reconstructed phase as either observed by experiment or proposed by theory. (C) 2010 Elsevier B.V. All rights reserved