Structural and Electrochemical Characterization of Metastable PtAu Bulk and Surface Alloys Prepared by Crossed-Beam Pulsed Laser Deposition

Crossed-beam pulsed laser deposition in a moderate He background gas pressure was used to prepare PtAu thin films. The Pt bulk content was determined by neutron activation analysis, whereas X-ray diffraction and X-ray photoelectron spectroscopy were used to assess the bulk and the surface structure of the films, respectively. It is shown that metastable PtAu alloys with a unique fcc structure are formed over the whole composition range. The surface composition of the films closely follows the bulk content, and X-ray photoelectron spectroscopy reveals that the surface of the films is also made of a PtAu alloy. These films are stable under ambient conditions. The electrochemical properties of these films were determined by cyclic voltammetry in H2SO4 electrolyte, and their reactivity toward the electrooxidation of CO and the electroreduction of O2 was assessed. The CO stripping peak potential value increases with the Au content, indicating an increased binding energy in comparison with polycrystalline Pt. Similarly, there is a cathodic shift of the Pt oxide reduction peak for the Au-rich alloy that indicates stronger Pt−O binding energies as compared with Pt-rich alloy electrodes. At the surface, the presence of Au in close proximity to Pt atoms induces a shift of the d-band center of the Pt atoms that translates into stronger bonds with CO- and O-containing species at the surface of the samples. As far as we can tell, the surface composition and structure of the deposits are not modified following the electrochemical measurements.