Surface reactivity of Pd nanoparticles supported on polycrystalline substrates as compared to thin film model catalysts:: Infrared study of CO adsorption

To identify the nature and the local structure of the surface of supported catalyst nanoparticles, we have performed a detailed comparative study of CO adsorption on two categories of oxide-supported Palladium catalysts: (1) polycrystalline MgO and gamma-Al2O3 supported Pd metal catalysts prepared by impregnation techniques and characterized by different degrees of regularity and perfection and (2) single-crystal based Pd model catalysts prepared under ultrahigh vacuum (UHV) conditions. The assignment of the CO vibrational frequencies to different types of sites on these systems has allowed a detailed structural characterization. For the Pd model catalyst, at low CO coverage, the infrared (IR) reflection absorption spectra closely resemble the expected behavior for terminations by a majority of (111) facets and a minority of (100) facets. The spectral features are indicative of defect sites such as particle steps and edges. Occupation of the defect sites can be affected by surface contaminations such as atomic carbon. Thus the CO spectra at high coverage can be used as both a structural and chemical probe under reaction conditions, provided that complementary information on the particle morphology is available. For the MgO and gamma-Al2O3 supported Pd systems, two distinct narrow bands (v congruent to 2070 and congruent to 1970 cm(-1)) have been assigned to linearly bonded and bridge-bonded CO species, on Pd (100)/(111) edges or facets, in agreement with the previous results obtained on model catalysts. The broad character of the 2070 cm(-1) feature indicates the simultaneous presence of (100) and (111) faces, with edge and corner sites present at their intersection. The high intensity and the small half-width (fwhm) of the band at 1970 cm(-1) on a Pd/MgO sample treated at high temperature, assigned to bridge-bonded CO species, suggests that the metal particles expose faces with a high level of regularity. Further spectroscopic features (v congruent to 1920-1800 cm(-1)), are ascribed to the presence of different types of 3-fold hollow sites on (111) faces.