Microstructure and NO decomposition behavior of sol-gel derived (La0.8Sr0.2)0.95MnO3/yttria-stabilized zirconia nanocomposite thin film

(La_0.8Sr_0.2)_0.95MnO₃ and (La_0.8Sr_0.2)_0.95MnO₃/YSZ gel films were deposited by a spin-coating technique on scandium-doped zirconia (ScSZ) substrate using the precursor solution prepared from La(Oi-C₃H₇)₃, Sr(Oi-C₃H₇)₂, Mn(Oi-C₃H₇)₂ and 2-methoxyethanol. By heat-treating the gel films, the membrane reactors, (La_0.8Sr_0.2)_0.95MnO₃|ScSZ|Pt and (La_0.8Sr_0.2)_0.95MnO₃/YSZ|ScSZ|Pt were fabricated. It was found that the pre-firing temperature affected the microstructure evolution of (La_0.8Sr_0.2)_0.95MnO₃ and (La_0.8Sr_0.2)_0.95MnO₃/YSZ thin films. Pre-firing at low temperature resulted in high porosity and large grain size of the thin films. NO decomposition characteristics of the obtained membrane reactors were investigated at 600 °C in reactant gas, 1000 ppm of NO and 2% of oxygen. By applying a direct current to the membrane reactors, NO can be decomposed at the (La_0.8Sr_0.2)_0.95MnO₃ and (La_0.8Sr_0.2)_0.95MnO₃/YSZ composite cathode. By incorporating YSZ into (La_0.8Sr_0.2)_0.95MnO₃, the required consuming power to decompose NO could be reduced.     

Emulsion processing of SOFC materials Ca0.3La0.7CrO3, Sr0.16La0.84CrO3, and Sr0.2La0.8MnO3

A novel preparation route to the perovskite materials Ca_0.3La_0.7CrO₃, Sr_0.16La_0.84CrO₃, and Sr_0.2La_0.8MnO₃ is described. The method produces the phase pure perovskite phases after calcination at 700°C for 2 hours. The powders produced are unagglomerated, and consist of hollow spherical particles 0.15 m in diameter. EDX has shown that the careful control of reaction conditions is vital to control the phase composition, and that small changes in stoichiometry result in the production of unsinterable powder.     

Low-Temperature Synthesis of Ultrafine La0.7Sr0.3MnO3 Powder via Chelate Homogenization

Ultrafine La_0.7Sr_0.3MnO₃ powders were prepared via homogenization in chelate solutions, followed by the calcination of solid precursors at 700°C in air or oxygen, and their phase composition and average particle size were determined. The solid precursors were obtained from a solution of polynuclear La, Sr, and Mn chelates (diethylenetriaminepentaacetates) by three procedures: (1) gelation of the solution, followed by air drying of the resultant gel; (2) gelation followed by microwave dehydration; and (3) microwave dehydration of the solution. The results demonstrate that the way in which the chelate solution is converted into solid foams has little effect on the phase composition and particle size of the powders. At the same time, the phase composition and particle size of the reaction products depend on the calcination atmosphere (air or oxygen). Calcination in oxygen (700°C, 10 h) ensures the preparation of phase-pure La_0.7Sr_0.3MnO₃ powders, with an average particle size of 30 nm, from the three precursors.     

Transmission electron microscopy study of multilayer p-n hetero-junction La0.9Sr0.1MnO3/SrNb0.05Ti0.95O3 thin films

We have fabricated multilayer p-n hetero-junction structure La_0.9Sr_0.1MnO₃/SrNb_0.05Ti_0.95O₃ colossal magneto-resistivity thin films. The observations of transmission electron microscopy showed that the interfacial structure between La_0.9Sr_0.1MnO₃ and SrNb_0.05Ti_0.95O₃ was of great epitaxy and atomic level smooth. There was a superstructure within La_0.9Sr_0.1MnO₃ thin films which was clarified in terms of the ordered partial substitution of La with Sr at center body of unit cell. Its chemical composition and distribution information investigated by electron energy loss spectrum and element mapping in the multilayer thin films were discussed.     

Investigation of strontium-doped La(Cr,Mn)O3 for solid oxide fuel cells

The (La, Sr) (Cr, Mn)O₃ system was investigated in an effort to develop an interconnect and cathode materials for solid oxide fuel cells. Sintering studies were done in air at temperatures below 1500°C. Significant improvements in densification were observed with substitution of 50 mol% Mn for chromium and a density of 95% theoretical was achieved with the substitution of 70 mol% Mn for chromium in the La(Cr, Mn)O₃ system. Electrical conductivity (d.c.) measurements were made as a function of temperature and oxygen activity. At 1000°C and 1 atm oxygen, the electrical conductivity ranged from 2.2–20 S cm^–1 for LaCr_0.8Mn_0.4O₃ and La_0.9Sr_0.1Cr_0.2Mn_0.8O₃, respectively. All of the compositions showed similar dependence of electrical conductivity on the oxygen activity. Dependence was small at high oxygen activities; as the oxygen activity decreased, a break in electrical conductivity at 10^–12 atm and 1000°C was observed, and then the electrical conductivity decreased asP _O2 ^1/4 . Sintering and electrical conductivity studies indicate that La_0.9Sr_0.1Cr_0.2Mn_0.8O₃ appears to be a candidate for solid oxide fuel cell applications.     

Structures and properties of La1−x,Sr x CoO3−y,prepared by freeze drying

Several samples of La_1–x Sr _x CoO_3–y (x = 1, 0.8, 0.5, 0.2) were prepared by calcining freezedried, stoichiometric mixtures of nitrates at different temperatures and for different lengths of time. Selected samples were characterized by powder X-ray diffraction, conductivity measurements, Brunauer-Emmett-Teller surface area measurement, and by electrochemical cyclic voltammetry in alkaline solutions and alkaline solutions containing methanol. The structures of each composition were complex and varied with composition and preparation conditions. There is evidence for non-stoichiometry caused by oxygen anion vacancies. For La_0.5Sr_0.5CoO_3–y the electrochemical activity towards the oxidation of methanol is a maximum at the fully formed cubic perovskite. The oxidation currents at La_0.8Sr_0.2CoO_3–y and La_0.2Sr_0.8CoO_3–y go through maxima at more distorted structures.     

Synthesis of La0.5A0.5MnO3 (A = Sr, Ba) by a hydrothermal method at low temperature

A mild hydrothermal method has been adopted to prepare La_0.5Sr_0.5MnO₃ and La_0.5Ba_0.5MnO₃, which is of interest for a number of possible applications. The results from X-ray diffraction (XRD) indicate that in the present work the temperature of 200 and 240 °C are sufficient to prepare phase pure La_0.5Sr_0.5MnO₃ and La_0.5Ba_0.5MnO₃ crystals. At 200 °C, La_0.5Sr_0.5MnO₃ nanowires are obtained. The average width and length of the nanowires are 40 nm and 4 μm, respectively. At 240 °C, La_0.5Ba_0.5MnO₃ powders obtained have a cubic structure with the average size of 3-5 μm.     

Effects of thermal treatment on the catalytic properties of LaCoO3 and La0.8Sr0.2CoO303

The effects of annealing temperature on the catalytic properties for CO oxidation and the surface state have been investigated with X-ray photoelectron spectroscopy in LaCoO₃ and La_0.8Sr_0.2CoO₃ compounds. The catalytic activity in both LaCoO₃ and La_0.8Sr_0.2CoO₃ depended on the ionicity between the surface cobalt and lattice oxygen. The change of ionicity on the surface can be explained by the change of Co-0 separations in the bulk.     

Dilution effects on X-ray photoelectron spectra of La<Subscript>0.8</Subscript>Sr<Subscript>0.2</Subscript>MnO<Subscript>3</Subscript> with SiO<Subscript>2</Subscript>

Diluted samples of La_0.8Sr_0.2MnO₃ with SiO₂ were prepared by calcination of the MCM-41 molecular sieve soaked in precursor solutions with various concentrations (0.1, 0.05 and 0.005 mol/l). The diluted samples from the 0.1, 0.05 and 0.005 mol/l solutions showed ferromagnetic behavior in temperature dependent magnetic susceptibility below 300, 250 and 100 K, respectively. The electron binding energy of the La 3d_5/2 main peak of the diluted samples from the 0.1, 0.05 and 0.005 mol/l solutions were 835.7, 836.0 and 837.4 eV, respectively, and were larger than that of La_0.8Sr_0.2MnO₃ bulk sample (834.2 eV). Reduction in intensity of the La 3d charge-transfer satellite was more pronounced for more diluted sample. The Mn 2p_3/2 main peak of all the diluted samples remained at 642.2 eV, which is larger by 0.6 eV than that of the bulk sample (641.6 eV). The charge-transfer peak energy in the optical absorption spectra was the same (2.3 eV) for all the diluted samples, and the energy was larger by 0.4 eV than the bulk one (1.9 eV). The dilution caused localization of charge carriers within the La_0.8Sr_0.2MnO₃ lattices isolated by the insulator. Suppression of charge flow between the isolated La_0.8Sr_0.2MnO₃ lattices resulted in the enlargement of the La 3d electron binding energy and the decrease of the La 3d charge-transfer satellite peak intensity, and also the lowering of the ferromagnetic ordering temperature. © Springer Science + Business Media, Inc.     

Combined platinum/perovskite catalyst for an efficient nanostructured air electrode

This work shows the stepwise improvement of air electrodes by the right combination of catalysts. In all electrodes carbon nanotubes serve as carbon support. The electrodes are produced by ultrasonic mixing of the carbon nanotubes and the catalysts. Their catalytic activity towards oxygen reduction in alkaline solution is evaluated by polarisation curves and electrochemical impedance spectroscopy. In a first step La_1?xSr_xMnO₃ perovskites are investigated, as well as La_0.65Sr_0.35MnO₃ and La_0.6Sr_0.4CoO₃ are compared. It is found that La_0.65Sr_0.35MnO₃ and La_0.6Sr_0.4CoO₃ have a positive impact on different parts of the current–potential curve. In a second step the influence of small amounts of platinum as an additional catalyst besides the perovskite is analyzed with the result that platinum lowers significantly the activation polarisation. Finally, the optimum composition of the electrode is found by using the synergetic effect of platinum, La_0.65Sr_0.35MnO₃ and La_0.6Sr_0.4CoO₃.     

Electrical Resistivity of La0.7Sr0.3MnO3 Ceramics Prepared via Chelate Homogenization

La_0.7Sr_0.3MnO₃ ceramics are prepared from powders produced via gelation and/or microwave processing of solutions of polynuclear chelates (La, Sr, and Mn diethylenetriaminepentaacetates), and their electrical resistivity is measured as a function of temperature. As the sintering temperature is raised from 800 to 1100°C, the average grain size of the ceramics, evaluated by the Debye–Scherrer method, increases by about a factor of 2.5 and their resistivity drops by about two orders of magnitude. The effect of the sintering temperature on the average grain size depends very little on the preparation procedure. For some of the samples, the room-temperature weak-field magnetoresistance is determined.     

Effect of Y-doping on the transport and magnetic properties of La0.5Sr0.5CoO3 and La0.7Sr0.3CoO3

The temperature variation of magnetization, resistivity, and thermoelectric power of undoped and Y-doped La_0.7Sr_0.3CoO₃ and La_0.5Sr_0.5CoO₃ samples have been investigated. Y-doping decreases the magnetization possibly due to the spin-state transition of Co ions. The low temperature conduction in (La_1?y Y _y )_0.7Sr_0.3CoO₃ is consistent with the variable range hopping. With Y-doping, value of the Seebeck coefficient increases as Y-doping decreases bandwidth and increases distortion. Seebeck coefficient value also reflects that the orbital stability increases with Sr concentration.     

Proton conduction in La0.9Sr0.1Ga0.8Mg0.2O3−α ceramic prepared via microemulsion method and its application in ammonia synthesis at atmospheric pressure

The popular electrolyte of La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−α was prepared via microemulsion method by using (NH₄)₂CO₃–NH₄OH as the co-precipitation reagent, followed by calcination and sinteration in air. The sintered ceramic was characterized by scanning electron microscopy (SEM) and powder X-ray diffraction (XRD) methods. The conduction behaviors in La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−α were investigated by using the electrochemical methods including gas concentration cells and electrochemical hydrogen permeation. The results indicate that the charge carriers in La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−α are protons under hydrogen atmosphere. Ammonia was synthesized at atmospheric pressure successfully by using La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−α as solid electrolyte for the first time.     

Structural, magnetic, infrared and Raman studies of La0.8Sr x Ca0.2-x MnO3 (0 ≤ x ≤ 0.2)

We report the results of magnetic, X-ray powder diffraction, infrared and temperature dependent Raman spectra of the La_0.8Sr _x Ca_0.2-x MnO₃ (0 ≤ x ≤ 0.2) manganite. The structure refinement using the Rietveld method indicates that the partial substitution of strontium for calcium (for x ≥ 0.15) modifies the orthorhombic structure of the CaMnO₃ perovskite towards a rhombohedral phase. Magnetic measurement confirms the increase in the Curie temperature from 180 K for La_0.8Ca_0.2MnO₃ to 307 K for La_0.8Sr_0.2MnO₃, respectively. It is argued that the substitution with the larger Sr²⁺ ion strengthens the double-exchange interaction and gives rise to the observed increase of transition temperatures. All manganites show two IR active vibrational modes around 400 and 600 cm^?1. Moreover, when x ≤ 0.1, the absorption band around 400 cm^?1 splits into two peaks. In addition, we have analyzed the frequencies and widths of the observed Raman modes as a function of temperature for all samples with various Sr content. The mode splitting is attributed to both magnetic ordering and large orthorhombic distortion in doped rhombohedral manganites.     

X-ray Photoelectron Spectra of La0.8 – x Ce x Sr0.2MnO3

La_{0.8 – x} Ce _x Sr_0.2MnO₃ (x= 0–0.3) mixed-conducting manganites are studied by x-ray photoelectron spectroscopy. The effect of A-site Ce substitution on the surface composition of the samples, charge states of the constituent cations, and bonding configuration is analyzed. The binding energies of the constituent elements are determined. The spectral shapes of the O 1s, La 4d, La 3d, Sr 3d, Mn 2p, Ce 4d, and Ce 3d peaks are examined as a function of Ce content.     

Synthesis of Ultrafine-Particle La0.7Sr0.3MnO3 via Chelate Homogenization and Microwave Processing

Ultrafine La_0.7Sr_0.3MnO₃ powders were prepared via homogenization in chelate solutions, followed by microwave dehydration, using polynuclear heterometallic diethylenetriaminepentaacetates as precursors. To assess the effect of the dehydration procedure on the phase composition and grain size of La_0.7Sr_0.3MnO₃ ceramics, three routes were tested: concentration of chelate solutions by evaporation until the formation of a glassy precursor, microwave dehydration of chelate solutions, and a combination of gelation and microwave dehydration. Phase-pure La_0.7Sr_0.3MnO₃ with a crystallite size of 30–40 nm (as determined by transmission electron microscopy) could be obtained via microwave dehydration of heterobimetallic precursor solutions, followed by calcination at a temperature as low as 800°C.     

Crystal Structure and Magnetic Properties of (La1?xSrxMnO3)N(LaCrO3)1?N Solid Solutions

Solid solutions (La_1−x Sr _x MnO₃) _N (LaCrO₃)_1−N with (La, Sr) and (Mn, Cr) two types of substitutions have been synthesized. For all investigated compounds the valent state of Mn, probed by XPS, remains Mn³⁺, while oxygen valent state changes according to (La, Sr)-substitution. Both crystal structure analysis and magnetic properties demonstrate inhomogeneous state of investigated materials. PACS codes: 61.10.N 75.30.C 79.60     

Enhancement of bifunctional catalysis by Ir doping of La0.6Ca0.4CoO3 perovskites

La_0.6Ca_0.4Co_0.8Ir_0.2O₃ was prepared by solid state reaction synthesis from mixtures of La(NO₃)₃·6H₂O, Ca(NO₃)₂·4H₂O, Co(NO₃)₃·6H₂O, and IrO₂ at stoichiometric ratio. Images from scanning electron microscopy on the as-synthesized powders exhibited particles in irregular shape at 100-250 nm in size. X-ray diffraction analysis confirmed the formation of perovskite without the rutile signals from IrO₂, suggesting successful incorporation of Ir⁴⁺ at the Co cation sites. The carbon nanocapsules (CNCs) were used as an electrocatalyst support. Electrodes for electrochemical measurements were fabricated by depositing mixtures of CNCs, La_0.6Ca_0.4Co_0.8Ir_0.2O₃, and polymeric binders on commercially available noncatalyzed gas diffusion electrodes. In alkaline electrolyte, the La_0.6Ca_0.4Co_0.8Ir_0.2O₃/CNCs demonstrated superior performances than those of La_0.6Ca_0.4CoO₃/CNCs and IrO₂/CNCs in both charging and discharging current-potential polarization measurements.     

Substitution induced B-cation ordering in solid oxide fuel cell ceramics: (La0.8Sr0.2)(M0.9Ni0.1)O3 (M = Mn, Cr)

Perovskites are important materials in a number of important technological applications, including solid oxide fuel cells, catalysis, and giant magneto-resistance materials. For many of these purposes, a mixture of B-cations can be used to tune the desired properties, e.g., oxygen reduction, ionic conductivity. For a solid oxide fuel cell, two particular ceramic components are of critical importance and have been extensively studied, the cathode (La_0.8Sr_0.2)MnO_3−x and the interconnect material (La_0.8Sr_0.2)CrO₃. In this study, we examined the mixed B-cation perovskites (La_0.8Sr_0.2)(M_0.9Ni_0.1)O₃ (M = Mn, Cr). All materials were synthesized using the glycine-nitrate method, followed by air annealing. The structures were determined using powder neutron diffraction methods. Refinement of the data showed that even at this low concentration, the compounds have monoclinic symmetry (P2₁/n) and that the nickel had a strong preference for the smaller of the two octahedral sites. This small amount of nickel substituted on the B-site resulted in a symmetry reduction when compared to the unsubstituted (LaSr)MnO₃ or (LaSr)CrO₃ materials. Although this structural type has been seen previously in heavily substituted perovskites, these materials show that even at this low level of substitution a segregation of the metals in a manner similar to the double perovskites A₂BB′O_6−x can be detected. This may have implications involving material stresses on cycling that may result as the temperature is raised or lowered through this crystallographic transition.     

Synthesis, microstructure and dielectric properties of zirconium doped barium strontium titanate obtained by solvothermal method

(Ba_0.8Sr_0.2Zr_yTi_1?yO₃) (y = 0.05, 0.1, 0.15 and 0.2) nanosized powders is synthesized by solvothermal method. The formation of (Ba_0.8Sr_0.2Zr_yTi_1?yO₃) was confirmed by XRD, FT-IR and XPS analysis. The purity of the (Ba_0.8Sr_0.2Zr_yTi_1?yO₃) was examined using FT-IR spectroscopy. The X-ray analysis proves that all as-synthesized Ba_0.8Sr_0.2Zr_yTi_1?yO₃ powders have a cubic perovskite structure. The surface characterization indicates the powder contains Zr and Sr elements. SEM investigation shows that the average particle size is reduced with increasing the Zr content and the average particle size is in the range 37–50 nm, the well dispersed nano powders have narrow particle size distribution. The study of dielectric properties shows that the Curie peaks of dielectric constant become broader and shift towards lower temperature on the basis of Ba_0.8Sr_0.2TiO₃ and the dielectric loss decreases with increasing Zr content.