Temperature programmed desorption was used to study the reaction of CH3OH on several different
ceria-based model catalysts. These catalysts consisted of a CeO2(111) single crystal and thin ceria films
supported on α-Al2O3(0001) and yttria-stabilized zirconia (100). The results of this study demonstrate that
the reaction of CH3OH on CeO2 surfaces is highly structure sensitive and depends on crystallographic
orientation, the concentration of surface oxygen vacancies, and the oxidation state of surface cerium cations.
The primary decomposition pathway for methoxide intermediates adsorbed on surface oxygen vacancy
sites is dehydrogenation to produce H2CO and surface hydroxyl groups. The surface hydroxyl groups then
either react with additional methoxides to reform CH3OH or react to produce H2O. In contrast, methoxides
adsorbed on partially reduced ceria surfaces, possibly on Ce3+ sites, undergo complete dehydrogenation
to CO and H2.
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