Carbon Dioxide Adsorption on CeO2(110): An XPS and NEXAFS Study

The adsorption of CO2 on the surface of a CeO2(110) bulk single crystal was studied by X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The high-quality XPS and C K-edge NEXAFS data show that CO2 adsorbs as a carbonate species on both fully oxidized CeO2(110) and partially reduced CeO2-x(110). No evidence for the formation of a carboxylate (CO2 delta-) intermediate could be found. On the fully oxidized CeO2(110) substrate, the carbonate decomposes upon heating to above 400 K, leading to the desorption of CO2. The NEXAFS data reveal the presence of a minor amount of formate (or carboxylate) and bicarbonate species, which are related to reactions of CO2 with surface hydroxyl groups. In the case of reduced CeO2-x(110), the carbonate species completely disappear upon heating to temperatures above 500 K. In contrast to conclusions presented in earlier works, the oxidation state of the surface is unchanged, that is, CO2 does not re-oxidize the reduced CeO2-x(110) surface.