EFFECT OF LANTHANUM MANGANITE MODIFICATION BY CALCIUM AND/OR FLUORINE ON THE BONDING STRENGTH, MOBILITY AND REACTIVITY OF THE LATTICE AND SURFACE OXYGEN

ABSTRACTCa and/or F-modified samples of LaMnO3 have been prepared by the Pechini method. The bulk structure of samples was characterized by TEM, EXAFS and XRD, while the surface composition was studied by SIMS. Thermal analysis, O2 TPD, H2 TPR and isothermal pulse/flow samples reduction by CO were applied to characterize the accessible surface/bulk oxygen mobility and reactivity. A reasonable description of the experimental energetic spectrum of the surface oxygen for various types of regular and defect surface sites on the perovskite faces was achieved by using semiempirical Interacting Bonds Method in the slab approximation with a due regard for the surface face termination and relaxation. Fluorine was found to decrease the surface coverage by reactive weakly bound oxygen forms while increasing the bulk oxygen excess and mobility. Calcium generated reactive weakly bound oxygen forms while decreasing the oxygen excess in the lattice and converting the regular M-O oxygen forms into the bridging ones through migration to the surface.