Comparative study of SO2 adsorption on metal oxides

SO2 adsorption on different metal oxides (MgO, CeO2, ZrO2, MgAl2O4, TiO2-anatase, TiO2-rutile, Al2O3 and Na–Al2O3) has been studied using various techniques (thermogravimetry, temperature-programmed desorption, IR spectroscopy). Several types of species are formed and the results are discussed in terms of their thermal stability. Weakly adsorbed species can result from the coordination of SO2 on Lewis acid sites such as Al2O3 or TiO2. However, such interactions are quite weak. On more basic oxides, such as Na–Al2O3, SO2 acts as an electron acceptor and adsorbs on either weakly basic O2– sites or on the basic OH– groups. In this latter case, the formation of hydrogen sulfite species is suggested. More strongly adsorbed species occur on all the oxides. These are characterized by strong absorption bands between 1100 and 800 cm–1, and are due to sulfite species. Several types generally occur. Gravimetric measurements allow us to compare the thermal stability and the amount of the different types of adsorbed SO2 species. The quantity of SO2 irreversibly adsorbed after evacuation at T < 370 K gives rise to an evaluation of the number of basic sites and therefore to a scale of basicity of the different oxides.The results are compared with those obtained using other probe molecules such as carbon dioxide or hexafluoroisopropanol. A special case is that of ceria for which it is observed that heating under vacuum transforms sulfite species into sulfates, preventing the use of TPD for the determination of its relative basicity.