Correlation between surface chemistry and morphology of PtCu and Pt nanoparticles during oxidation-reduction cycle

Process conditions during catalytic reactions induce significant changes in surface chemistry and structure of bi- (mono) metallic nanoparticles leading to their deactivation, and this can ultimately affect the reactions long-term performance. Here PtCu and Pt model nanoparticles are prepared by microwave synthesis and characterized by X-ray diffraction (XRD). Surface chemical and morphological changes of the nanoparticles during high-temperature oxidation and reduction treatments cycle are correlated by near in situ X-ray photoelectron spectroscopy (XPS) and ex situ transmission electron microscopy (TEM) - energy-dispersive X-ray spectroscopy (EDS) studies. At 300 °C the surface atomic composition of the PtCu nanoparticles switches reversibly upon the cycle and at the same time their morphology and composition are maintained. At 400 °C, the surface atomic composition does not fully restore and, while the shape is maintained, the size and composition are not. This occurs by a mechanism of Cu leaching out from the nanoparticles. These data delineate potential operating conditions for stable PtCu nanocatalysts.