The interaction of tin with cerium oxide thin film and cerium oxide nanosized powder was studied using XPS and resonant photoelectron spectroscopy (RPES) in the Ce 4d-4f photoabsorption region. A strong tin-ceria interaction led to partial Ce 4+ → Ce 3+ transition and Sn + ion formation. A corresponding increase of the Ce 4f state occupancy was observed as a giant 4f resonance enhancement. In the case of powder catalyst a strong CeO 2 -Sn interaction lead to formation of Ce-Sn-O mixed oxide system characterized by Ce 3+ ion concentration enhancement and increase of Ce 4f occupation. It explains generally higher catalytic activity of the Ce-Sn-O mixed oxide catalysts when comparing with the individual oxides.
We have studied the adsorption of low dimensional gold on ceria, produced by evaporation onto the surface. The interaction of gold with CeO(2)(111) layers was investigated with x-ray photoemission spectroscopy, ultraviolet photoemission spectroscopy, and resonant photoelectron spectroscopy (RPES). Gold was deposited in steps onto a 1.5 nm thick CeO(2)(111) layer epitaxially grown on a Cu(111) substrate. The RPES showed a partial Ce(4+)-->Ce(3+) reduction, observed as a resonant enhancement of the 4f level of the Ce(3+) species. This can be explained by possible creation of a new Au(+) ionic state. The observed effects are stronger for Au deposition at room temperature than at 250 degrees C. The obtained results are in agreement with already published density functional theory calculations reporting weakening of bond between the oxygen and the Ce atoms in ceria caused by the presence of gold.
The interaction of gold with CeO2 layers was investigated using photoelectron spectroscopy. 65 nm thick Au doped CeO2 layers were deposited by rf-magnetron sputtering on a Si(0 0 1) substrate by using a composite CeO2–Au target. The laboratory XPS and synchrotron radiation soft x-ray and hard x-ray photoemission spectra showed the formation of stoichiometric Ce4+ (CeO2) and the appearance of new Au+,3+ states with ionized Au species in excess of 50% of the total Au amount. Depth resolved measurements, by varying the emission angle or photon energy, indicated the formation of an Au0 overlayer and deeper Au+,3+ species. The formation of Au+,3+ ions was found to be strongly dependent on the cerium oxide stoichiometry. The amount of ionized Au can be reversibly decreased and increased by surface reduction (removal of O by sputtering) and subsequent surface re-oxidation.
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