Abstract
Mobility and reactivity of the surface and bulk oxygen of perovskite-like mixed oxides including lanthanum manganite (I) and ferrite (II) systems modified by Ca (I,II) and fluorine (I), as well as some Co, Fe-containing complex perovskites were considered. Combination of thermal analysis data, oxygen isotope exchange, O2 TPD, reduction by CO, H2 and CH4 TPR, were applied to characterize the accessible surface/bulk oxygen mobility and reactivity. Comparison of these results with earlier data on the real (defect) structure of these systems by TEM, EXAFS, XRD, FTIRS, SIMS allowed to elucidate factors determining the oxygen mobility and reactivity. A quantitative description of the experimental energetic spectrum of oxygen bound with regular and defect surface sites of perovskites was obtained by using the semiempirical Interacting Bonds method with a due regard for the surface face termination and relaxation. Pronounced effect of cation vacancies on the activation barrier for the oxygen migration in the perovskite lattice has been revealed.
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