Structural and surface analysis of unsupported and alumina-supported La(Mn,Fe,Mo)O₃ perovskite oxides.

Rosmaninho, M. G.; Tristão, J. C.; Moura, F. C. C.; Lago, R. M.; Araújo, M. H.; Fierro, J. L. G.

A series of bulk and Al2O3-supported perovskite oxides of the type LaMn1 − x − yFe xMo yO3 ( x = 0.00−0.90 and y = 0.00–0.09) were synthesized by the citric acid complexation–gelation method followed by annealing in air at 800 °C. For all samples, the local environment and the chemical state and concentration of surface species were determined. Mössbauer spectra revealed the only presence of octahedral Fe3 ions dispersed in the perovskite structure, however well-crystallized together with a poorly crystalline LaFeO3 phases were detected for larger substitutions ( x = 0.90). A similar picture was obtained for Mo-loaded ( y = 0.02 and 0.05) samples but a new phase most likely related to Fe3 ions dispersed aside from the perovskite structure was found for larger substitutions ( y = 0.09). Together with these structures, supported samples showed the presence of LaFeO3 nanoparticles. Finally, photoelectron spectroscopy indicated that the chemical state and composition of the samples in the surface region (2–3 nm) approaches that of the bulk. For the unsupported substituted samples, iron (and molybdenum) enters into the perovskite structure while manganese tends to be slightly segregated. Moreover, in supported perovskites, a fraction of Mo and La atoms interact with the alumina surface. All these oxides were active in methane combustion and best performance was recorded for the Fe-rich composition ( x = 0.9) in which both Mn3 and Mo3 ions were in the same proportion ( y = 0.05).

PEROVSKITE; OXIDE minerals; ALUMINUM oxide; MOSSBAUER spectroscopy; METHANE; COMBUSTION; PHOTOELECTRON spectroscopy

Analytical & Bioanalytical Chemistry, 2010, Vol 396, Issue 8, p2785

1618-2642

Academic Journal

10.1007/s00216-009-3308-5