ABSTRACT
New polycrystalline SrMo1-xMxO4-δ (M = Fe and Cr) scheelite oxides have been prepared by topotactical oxidation, by annealing in air at 500 °C, from precursor perovskites with the stoichiometry SrMo1-xMxO3-δ (M = Fe and Cr). An excellent reversibility between the oxidized Sr(Mo,M)O4-δ scheelite and the reduced Sr(Mo,M)O3-δ perovskite phase accounts for the excellent behavior of the latter as anode material in solid-oxide fuel cells. A characterization by X-ray powder diffraction (XRD) and neutron powder diffraction (NPD) has been carried out to determine the crystal structure features. The scheelite oxides are tetragonal, space group I41/a (No. 88). The Rietveld-refinement from NPD data at room temperature shows evidence of oxygen vacancies in the structure, due to the introduction of Fe3+/Cr4+ cations in the tetrahedrally-coordinated B sublattice, where Mo is hexavalent. A thermal analysis of the reduced perovskite (SrMo1-xMxO3-δ) in oxidizing conditions confirms the oxygen stoichiometry obtained by NPD data; the stability range of the doped oxides, below 400-450 °C, is lower than that for the parent SrMoO3 oxide. The presence of a Mo4+/Mo5+ mixed valence in the reduced SrMo1-xMxO3-δ perovskite oxides confers greater instability against oxidation compared with the parent oxide. Finally, an XPS study confirms the surface oxidation states of Mo, Fe, and Cr in the oxidized samples SrMo0.9Fe0.1O4-δ and SrMo0.8Cr0.2O4-δ.
ABSTRACT
Sr0.7Ho0.3CoO3-δ oxide has been recently described as an excellent cathode material (1274 mW cm(-2) at 850 °C with pure H2 as fuel1) for solid oxide fuel cells (SOFCs) with LSGM as electrolyte. In this work, we describe a detailed study of its crystal structure conducted to find out the correlation between the excellent performance as a cathode and the structural features. The tetragonal crystal structure (e.g., I4/mmm) basically contains layers of octahedrally coordinated Co2O6 units alternated with layers of Co1O4 tetrahedra sharing corners. An "in situ" neutron power diffraction (NPD) experiment, between 25 and 800 °C, reveals the presence of a high oxygen deficiency affecting O4 oxygen atoms, with large displacement factors that suggest a large lability and mobility. Difference Fourier maps allow the visualization at high temperatures of the 2D diffusion pathways within the tetrahedral layers, where O3 and O4 oxygens participate. The measured thermal expansion coefficient is 16.61 × 10(-6) K(-1) between 300 and 850 °C, exhibiting an excellent chemical compatibility with the electrolyte.
ABSTRACT
The members of the family of pyrochlore oxides with the formula R(2)MnRuO(7) (R = Tb, Dy, Ho, Er, Tm, Yb, Lu and Y) have been synthesized and characterized. Polycrystalline samples were prepared by a soft chemistry procedure involving citrates of the different metal ions, followed by thermal treatments in air or O(2) pressure. The crystallographic and magnetic structures have been analysed from X-ray diffraction (XRD) and neutron powder diffraction (NPD) data, in complement with magnetic measurements; the evolution along the series of the crystallographic parameters (unit-cell parameters, bond distances and angles) is discussed. In R(2)MnRuO(7) pyrochlores, Mn and Ru ions statistically occupy the 16c sites in a cubic unit cell with space group Fd Ì 3m, which defines an intrinsic frustrated three-dimensional system. In all the cases, the low-temperature NPD data unveils an antiferromagnetic coupling of two subsets of Mn(4+)/Ru(4+) spins, indicating that the magnetic frustration is partially relieved by the random distribution of Mn and Ru over the 16c sites. At lower temperatures there is a polarization of the R(3+) magnetic moments, which also participate in the magnetic structure, when a magnetic rare earth is present.