Reactions of ethanol over CeO2 and Ru/CeO2 catalysts

• Ethanol reactions are studied over on Ru/CeO2 by TPD and steam reforming.
• Main reactions during TPD are dehydrogenation to acetaldehyde and dehydration to ethylene.
• The presence of Ru switched the desorption products to CO, CO2, CH4 and H2.
• Shift in reaction selectivity between CO2 and CO during TPD, linked to ESR, is due to WGSR.

The reaction of ethanol has been investigated on Ru/CeO2 in steady state conditions as well as with temperature programmed desorption (TPD). High resolution transmission electron microscopy (HRTEM) images indicated that the used catalyst contained Ru particles with a mean size of ca. 1.5 nm well dispersed on CeO2 (of about 12–15 nm in size). Surface uptake of ethanol was measured by changing exposure to ethanol followed by TPD. Saturation coverage is found to be between 0.25 and 0.33 of a monolayer for CeO2 that has been prior heated with O2 at 773 K. The main reactions of ethanol on CeO2 during TPD are: re-combinative desorption of ethanol; dehydrogenation to acetaldehyde; and dehydration to ethylene. The dehydration to ethylene occurs mainly in a small temperature window at about 700 K and it is attributed to ethoxides adsorbed on surface-oxygen defects. The presence of Ru considerably modified the reaction of ceria towards ethanol. It has switched the desorption products to CO, CO2, CH4 and H2. These latter products are typical reforming products. Ethanol steam reforming (ESR) conducted on Ru/CeO2 indicated that optimal reaction activity is at about 673 K above which CO2 production declines (together with that of H2) due to reverse water gas shift. This trend was well captured during ethanol TPD where CO2 desorbed about 50 K below than CO on both oxidized and reduced Ru/CeO2 catalysts.

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