RESUMO
The amorphous reduction product of the oxide ion conductor La2Mo2O9 was previously shown to be a good, sulphur-tolerant, anode material for solid oxide fuel cell devices (X. C. Lu, J. H. Zhu, J. Electrochem. Soc., 2008, 155(10), B1053). In this paper, we study the local order of amorphous La2Mo2O6.7 using X-ray absorption spectroscopy analyses and electronic paramagnetic resonance. The extended X-ray absorption fine structure analysis of local arrangements around Mo in La2Mo2O6.7 is first carried out on the basis of strong distortions from three crystalline models of La2Mo2O9, La7Mo7O30 and La2Mo2O7. The extended X-ray absorption fits obtained from both La2Mo2O9 and La7Mo7O30 yield similar atomic arrangements in the amorphous phase, upon large atomic displacements. However it is also possible to fit the spectrum using the paths of La2Mo2O7, in better agreement with EPR results suggesting the presence of Mo-Mo pairs. Simpler arrangements, built from theoretical single scattering paths, are considered. All models are discussed and compared. A most probable short range structure around Mo in this amorphous phase is proposed. It both fulfills EPR results and appears coherent with the presence of ionic conductivity.
RESUMO
The role of W content on the limit oxygen partial pressure (pO2) for stability of fast oxygen-ion conductors La2Mo2-yWyO9 with y = 0, 0.5 and 1.0 has been studied by means of thermogravimetric analysis (TGA) under controlled atmospheres. At 718 °C, below the pO2 stability limit of La2Mo2-yWyO9, the perovskite related compounds La7Mo7(2-y)/2W7y/2O30 were stabilized even for y = 1.0. At 608 °C, the first stage of reduction of ß-La2Mo2-yWyO9 leads to the formation of the crystallized oxygen deficient La2Mo2-yWyO8.6+0.02y phase. X-ray powder diffraction shows that the stabilization of the high temperature ß-form through tungsten substitution observed in fully oxidized La2Mo2-yWyO9 samples is preserved upon slight reduction. The n-type conductivity arising from the mixed valence state of molybdenum becomes less and less predominant as the W content increases. Further reduction causes amorphization. At both temperatures, W substitution does not enhance the thermodynamic stability of the La2Mo2-yWyO9 ion conductor under a reducing atmosphere but only slows down the kinetics of reduction.
RESUMO
Thermogravimetric analysis (TGA) technique in controlled oxygen partial pressure (pO(2)) atmospheres has been used to obtain equilibrium oxygen content data as a function of pO(2) on the La(2)Mo(2)O(9-δ) system resulting from the partial reduction of fast oxide-ion conductor La(2)Mo(2)O(9) (LM). Thermodynamic conditions for stabilization of crystalline La(7)Mo(7)O(30) and amorphous La(2)Mo(2)O(7-y) at 718 °C have been determined and discussed. At 608 °C, the compound reported for the first time La(2)Mo(2)O(8.96) (LM896) has been found. The crystalline form and transition temperature in LM896 have been identified by X-ray diffraction at room temperature (XRD) and at controlled temperature. Conductivity curves obtained by electrochemical impedance spectroscopy (EIS) as a function of temperature for both LM and LM896 have been compared. The results indicate that LM896 is a mixed ionic and electronic conductor (MIEC).