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Formation of meta-stable surface-alloys can be used as a way to tune the binding strength of reaction intermediates and could therefore be used as improved catalyst materials for heterogeneous catalysis. Understanding the role of adsorbates on such alloy surfaces can provide new insights for engineering of more active or selective catalyst materials. Dynamical surface changes on alloy surfaces due to the adsorption of reactants in high gas pressures are challenging to investigate using standard characterization tools. Here we apply synchrotron illuminated near ambient pressure X-ray photoelectron spectroscopy to probe the surface structure of a CuPt model system. We report an investigation of the formation of a CuPt surface alloy induced and stabilized by exposure to mbar pressures of CO. The location of Pt within the alloy is assessed by deconvolution of the Pt 4f core level spectra into surface Pt and bulk Pt contributions. The study provides direct evidence on how it is possible to monitor the surface structure under near operation conditions. (C) 2014 Elsevier B.V. All rights reserved. (Less)

Using temperature-programmed desorption experiments, we have studied the coordination dependent adsorption of CO on a platinum (Pt) single crystal, and mass-selected Pt nanoparticles in the size range of 3 to 11 nm, for CO dosing pressures in 10–7 mbar and mbar ranges. From low pressure CO adsorption experiments on the Pt(111) crystal, we establish a clear link between the degree of presputtering of the surface prior to CO adsorption, and the amount of CO bound at high temperature. It was found that for rougher surfaces, i.e., with more undercoordinated surface atoms, a feature appears in the CO desorption spectra at high temperature. The result is consistent with literature results from stepped single crystals that have found high temperature CO desorption features due to the presence of undercoordinated step and kink sites on the crystal facets. For the nanoparticles, a study of the dependence of the CO desorption profile with particle size found more prominent high temperature CO desorption features as...

The Pt(111)/electrolyte interface has been characterized during the oxygen reduction reaction (ORR) in 0.1 M HClO(4) using electrochemical impedance spectroscopy. The surface was studied within the potential region where adsorption of OH* and O* species occur without significant place exchange between the adsorbate and Pt surface atoms (0.45-1.15 V vs RHE). An equivalent electric circuit is proposed to model the Pt(111)/electrolyte interface under ORR conditions within the selected potential window. This equivalent circuit reflects three processes with different time constants, which occur simultaneously during the ORR at Pt(111). Density functional theory (DFT) calculations were used to correlate and interpret the results of the measurements. The calculations indicate that the coadsorption of ClO(4)* and Cl* with OH* is unlikely. Our analysis suggests that the two-dimensional (2D) structures formed in O(2)-free solution are also formed under ORR conditions.