Surface Segregation of Pd from TiO2-Supported AuPd Nanoalloys under CO Oxidation Conditions Observed In situ by ETEM and DRIFTS



A TiO2-supported AuPd bimetallic catalyst with an Au/Pd atomic ratio of 8 was prepared by deposition-precipitation with urea, and its activity in CO oxidation at room temperature was compared to the one of a monometallic Au/TiO2 catalyst. X-ray photoelectron spectroscopy (XPS) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analyses suggest that Au-Pd/TiO2 contains bimetallic nanoparticles after reduction under H2 at 500 °C although the presence of monometallic Au particles cannot be totally excluded. The evolution of the AuPd nanoparticles surface composition during exposure to O2 and CO/O2 was studied in situ by environmental high resolution electron microscopy (ETEM) and DRIFTS. Pd segregation at the surface of the bimetallic nanoparticles was evidenced by DRIFTS and directly observed by ETEM under O2 and CO/O2 with the formation of Aucore-Pdshell structure. The changes in the surface composition of the Au-Pd nanoparticles under CO/O2 was paralleled with the higher rate of deactivation in the first reaction stages observed for Au-Pd/TiO2 compared to Au/TiO2, which could be related to the possible replacement of Au in low coordination sites, at the origin of the high activity in CO oxidation, by Pd atoms. These results noticeably underline the modifications induced by the reactant that can undergo a bimetallic AuPd catalyst.