Journal of Physical Chemistry, Vol.99, No.39, 14437-14443, 1995
Silica-Supported Zirconia .1. Characterization by Infrared-Spectroscopy, Temperature-Programmed Desorption, and X-Ray-Diffraction
Silica-supported zirconia samples have been prepared by aqueous impregnation of a nonporous fumed silica with zirconyl nitrate giving 5, 10, or 20 wt % ZrO2 on SiO2 after calcining at 450 degrees C. The surface areas were comparable to that of the parent silica (200 m(2)/g), and IR spectra showed OH peaks characteristic of SiO2 and of monoclinic ZrO2. The intensity of the SiOH peak decreased with ZrO2 loading, and a new IR band near 945 cm(-1) was attributed to the formation of ZrOSi linkages. The ZrO2 is dispersed as clusters on SiO2, and free SiOH is still available even at the highest ZrO2 loading. X-ray diffraction shows either that SiO2/ZrO2 is amorphous or that the ZrO2 crystallites are too small to be detected. Infrared spectroscopy of adsorbed ammonia and pyridine have shown that sites for coordination exist on all mixed oxides and on pure ZrO2, The number of sites for coordination of NH3 increases as the ZrO2 loading increases, Moreover, there are very weak Bronsted acid sites on SiO2/ZrO2 which can protonate NH3; these are absent on ZrO2. Temperature-programmed desorption of adsorbed NH3 has shown that the number of sites available for coordination, protonation, or H-bonding to ZrOH is about 2.5-3-fold greater than the number of sites for H-bonding to SiOH groups on pure SiO2. Finally, IR of adsorbed CO2 (a probe of surface basicity) has shown that SiO2/ZrO2 is less basic than of pure ZrO2.
Keywords:OXIDE SURFACES;METAL-OXIDES;PHOTOELECTRON-SPECTROSCOPY;DEHYDROXYLATED SILICA;HYDROXYL-GROUPS;ZRO2 CATALYSTS;ACID SITES;ADSORPTION;AMMONIA;MODEL