Cationic Order-Disorder in Double Scheelite Type Oxides: the Case Study of Fergusonite La2SiMoO8.

Up to now, the possible occurrence of a cationic ordering on the tetrahedral sublattices of stoichiometric double scheelite-type oxides was not settled, with somewhat contradictory X-ray diffraction and optical measurements [Blasse, G. J. Inorg. Nucl. Chem. 1968, 30, 2091]. Using two different synthesis routes, both ordered and disordered forms of fergusonite La2SiMoO8 were prepared. The crystal structure of the ordered form was determined using powder X-ray and neutron diffraction, which clearly evidence a tridimensional ordering between [SiO4] and [MoO4] tetrahedra. The crystal chemistry of ordered double sheelite-type LaIII2(SiIVO4)(MoVIO4) can be seen as an intermediate between those of simple regular scheelite or fergusonite LnIII(NbVO4) and of ordered triple scheelite BiIII3(FeIIIO4)(MoVIO4)2. The structure of the disordered La2SiMoO8 phase was analyzed using powder X-ray diffraction. A few small and larger diffraction peaks or bumps are observed in addition to the sharper peaks of a simple fergusonite cell. DIFFaX and FAULTS programs helped showing that these faint peaks originate from stacking faults between 2D ordered layers. The intermediate 2D-3D nature of SiO4/MoO4 ordering in seemingly disordered compounds might explain the previous discrepancy between optical and X-ray diffraction measurements.

Reducing the thermal conductivity of La2Mo2O9 with a trivalent praseodymium substitution for its potential use as a thermal barrier coating.

(La1-xPrx)2Mo2O9 powders were synthesized by solid state reaction for x = 0.00, 0.10, 0.25, 0.50, 0.75 and 1.00. Dense pellets were obtained by conventional sintering in air. Their thermal stability and thermal conductivity were measured from 100 to 700 °C and their cell parameters refined from X-ray powder diffraction pattern by the Rietveld method. A 50 mol% isovalent substitution of lanthanum in La2Mo2O9 by praseodymium stabilizes the high temperature ß phase while reducing the thermal conductivity of the parent compound by 11-18%. For a praseodymium content x higher than 0.75, the thermal conductivity increases and a phase transition similar to that of La2Mo2O9 is observed except that the room temperature phase appears to be this time triclinic in symmetry.

Extension of the A nB nO3 n+2 Slicing/Oxidizing Process from 2D Layered to 1D Columnar Perovskites: The La7W7-xM xO30 Structural Family with Di-, Tri-, and Tetravalent Transition Metal M Substitutes to Tungsten.

The A7B7O30 structural type is a columnar-perovskite-type arrangement originally evidenced in La7Mo7O30 [Goutenoire et al. J. Solid State Chem. 1999, 142, 228], an intermediate reduction product of fast oxide-ion conductor La2Mo2O9. Subsequently, this new structural family has been extended to La7W6+4M5+3O30 (M = Nb, Ta) [Goutenoire et al. J. Solid State Chem. 2005, 178, 2811]. Here we show that it is possible to further extend the solid solution through partial substitution of hexavalent tungsten by di-, tri-, or tetravalent transition metals. The general formula is La3+7W6+7- xM m+ xO30 with x = 3/(6 - m), or m = 6 - 3/ x. Single phase samples with M m+ = Zn2+, Fe3+, and Ti4+ have been prepared, and their crystal structure refined using X-ray powder diffraction. In the structure, the transition metal with lower valence is preferentially located in the octahedral site shared by consecutive trans-connected perovskite cages, whose diagonal runs along the threefold axis of the structure. Close similarities are noticed with the cationic repartition and distortion of coordination polyhedra in compounds belonging to the A nB nO3 n+2 series of layered perovskites. A rationale is proposed, which includes the A7B7O30 structural type as a subsequent 1D step to the 3D → 2D A nB nO3 n+2 scheme of perovskite framework slicing by progressive oxygen insertion through decreasing n.

On the local order of amorphous La2Mo2O6.7.

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.

Cationic Intermixing and Reactivity at the La2 Mo2 O9 /La0.8 Sr0.2 MnO3-δ Solid Oxide Fuel Cell Electrolyte-Cathode Interface.

Among standard high-temperature cathode materials for solid oxide fuel cells, La0.8 Sr0.2 MnO3-δ (LSM) displays the least reactivity with the oxide-ion conductor La2 Mo2 O9 (LMO), yet a reaction is observed at high processing temperatures, identified by using XRD and focused ion beam secondary-ion mass spectrometry (FIB-SIMS) after annealing at 1050 and 1150 °C. Additionally, Sr and Mn solutions were deposited and annealed on LMO pellets, as well as a Mo solution on a LSM pellet. From these studies several reaction products were identified by using XRD and located by using FIB-SIMS on the surface of pelletised samples. We used depth profiling to show that the reactivity extended up to ∼10 µm from the surface region. If Sr was present, a SrMoO4 -type scheelite phase was always observed as a reaction product, and if Mn was present, LaMnO3+δ single crystals were observed on the surface of the LMO pellets. Additional phases such as La2 MoO6 and La6 MoO12 were also detected depending on the configuration and annealing temperature. Reaction mechanisms and detailed reaction formulae are proposed to explain these observations. The strongest driving force for cationic diffusion appears to originate from Mo(6+) and Mn(3+) cations, rather than from Sr(2+) .

Reduction Kinetics of La2Mo2O9 and Phase Evolution during Reduction and Reoxidation.

An amorphous reduced form of oxide ion conductor La2Mo2O9 had been proposed as sulfur-tolerant anode material for solid oxide fuel cell, but its oxygen content was not known. In this paper, we investigate the reduction kinetics by diluted hydrogen of La2Mo2O9 to amorphous, and the oxygen range of the amorphous form. The reduction kinetics is studied as a function of the powder specific surface area and of the temperature, on powders synthesized by solid state reaction and by polyol process using two different solvents. The reduction process was carried out by TGA under 10% H2 diluted in argon, and its kinetics is analyzed and modeled. As expected, small particles and high temperature lead to higher reduction rates. Several reduction steps were identified by XRD during the process. At 700 °C La2Mo2O9 is directly reduced into the amorphous phase La2Mo2O7-y, whereas at 760 °C reduction occurs through an intermediate crystallized La7Mo7O30 (≅ La2Mo2O8.57) phase before amorphization. In both cases, further reduction of La2Mo2O6.2 amorphous phase leads to an exsolution of metallic molybdenum and a molybdenum deficiency in the amorphous phase. Reoxidation of amorphous La2Mo2O7-y was studied by TGA, DTA and XRD. At low temperature in air, the reduced compounds are reoxidized while remaining amorphous. The annealing for 60 h at 350 °C in air of reduced La2Mo2O6.66, obtained beforehand by solid state reaction, gives an amorphous phase with composition La2Mo2O8.85. The existence domain of the reduced amorphous phase in terms of oxygen content therefore ranges at least from O6.2 to O8.85, thus including the composition La2Mo2O8.50 of the amorphous surface layer at the origin of a huge increase of ionic conductivity recently reported in nanowires of La2Mo2O9.

Thermodynamic stability of La2Mo2-yWyO9, La2Mo2-yWyO8.96+0.02y and La7Mo7(2-y)/2W7y/2O30 (y = 0, 0.5 and 1.0).

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.

Thermodynamic stability, structural and electrical characterization of mixed ionic and electronic conductor La2Mo2O(8.96).

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).

Analysis of the local structure of phosphorus-substituted LAMOX oxide ion conductors.

The effect of partial substitution of molybdenum by phosphorus on the global and local structural arrangement of the fast oxide-ion conductor La(2)Mo(2)O(9) (LAMOX) has been studied by X-ray powder diffraction as well as (139)La and (31)P solid state NMR. The diffraction patterns show that La(2)Mo(2-y)P(y)O(9-y/2) forms a solid solution at low phosphorus concentrations, and that there is a structural phase transition upon increasing phosphorus concentration. This phase transition is also reflected in (139)La and (31)P NMR spectra. The possibility to excite (31)P multiple-quantum coherences of one of the (31)P NMR signals gives evidence of an accumulation of phosphorus atoms on neighbouring Mo-type sites already before formation of three-dimensional precipitates. On the basis of our X-ray and NMR results we propose a possible structural arrangement of the compound La(2)Mo(2-y)P(y)O(9-y/2) that explains the experimental observations by crystal twinning.

Topological metastability and oxide ionic conduction in La(2)-(x)Eu(x)Mo(2)O(9).

The effect of partial substitution, up to x = 0.4, of La by trivalent Eu on the phase stability, thermal expansion, and transport properties of La2Mo2O9 are investigated using temperature-controlled X-ray powder diffraction, differential thermal analysis, and complex impedance spectroscopy. At low europium content (x < or = 0.1), the alpha-beta phase transition is observed at a temperature dependent on the sample shaping (powder, pellet, etc.). At high europium content (x > or = 0.25), the samples remain cubic (beta phase), regardless of the shaping. In the intermediate range of europium content (x = 0.15, 0.2), the phase stability is highly sensitive to the thermal history and the sample shaping, with a double-reversed beta-alpha-beta transition suppressed by the shaping/sintering process. The influence of the amount of europium on the transport mechanisms and parameters is studied in both low- (Arrhenius) and high-temperature (Vogel-Tammann-Fulcher = VTF) regimes. If the effect of substitution is rather mild and monotonous within each transport regime and crystallographic phase, an abrupt change in the Arrhenius parameters between the alpha- and beta-type phases is observed.

On the flexibility of the structural framework of cubic LAMOX compounds, in relationship with their anionic conduction properties.

A mathematical analysis of the cubic crystal structure of fast oxide-ion conductor beta-La(2)Mo(2)O(9) (and derived members of the LAMOX family) shows that its cationic sublattice can behave as a semirigid framework. Tilt/rotation of rigid [O1La(3)Mo] anti-tetrahedral units about their 3-fold axis can open up tunnels in the cationic framework, therefore favoring the mobility of O2 and O3 oxide ions located in these tunnels, as confirmed by molecular dynamics simulations. Such a process is likely to assist the anionic transport and explain the postulated transition from Arrhenius-type to VTF (Vogel-Tamman-Fulcher)-type behavior propounded to account for the peculiar conductivity curvature observed at high temperature in all the cubic LAMOX compounds. It also clarifies the correlated extra cell volume expansion observed at the same temperature in all these materials.

17O NMR in room temperature phase of La2Mo2O9 fast oxide ionic conductor.

A room temperature (17)O NMR study of La(2)Mo(2)O(9), a fast oxide ionic conductor exhibiting a phase transition at 580 degrees C between a low-temperature alpha-phase and a high-temperature beta-phase, is presented. Four partly overlapping quasi-continuous distributions of oxygen sites are evidenced from 1D magic angle spinning (MAS) and 2D triple quantum MAS NMR experiments. They can be correlated with the three oxygen sites O1, O2 and O3 of the high-temperature crystal structure. The low-temperature phase is characterized by two distributed sites of type O1, which proves that the symmetry is lower than in the cubic high-temperature phase. Two-dimensional experiments show that there is no dynamic exchange process, on the NMR time-scale, between the different oxygen sites at room temperature, which agrees well with conductivity results.