Coulometric Titration Studies of Nonstoichiometric Nanocrystalline Ceria

ABSTRACTOxygen nonstoichiometry measurements in nanocrystalline ceria, x in CeO2-x, were performed using coulometric titration. The measurements reveal large apparent deviations from stoichiometry, of the order of 10−3 − 10−4 at T = 405 − 455 °C and Po2 = 0.21 − 10−5 atm, as compared to levels of ∼10−9 for coarsened materials under the same conditions. The level of nonstoichiometry is, however, larger then expected from previous electrical conductivity data of nanocrystalline ceria. In addition, x ∝ Po2−½ while Σ ∝po2−1/6. The observed dependence of x(Po2, T) can be explained by either the formation of neutral oxygen vacancies at or near the interface, or by surface adsorption.