Crystal structure and electrical properties of new tungsten bronzes: BxWO3 (0.01 ≤ x ≤ 0.08)

Boron tungsten bronzes B_xWO₃ (0.01 ≤ x ≤ 0.08) were synthesized by hybrid microwave method from mixtures of WO₃ and amorphous boron powder. With the increase of boron content, the crystal structure of B_xWO₃ transforms from orthorhombic (x = 0.01) to tetragonal α (x = 0.048) and then to tetragonal β (0.07 ≤ x ≤ 0.08). The average size of crystallites is in the range of 1-10 μm. All samples show semiconducting behaviour in their temperature dependence of resistivity. The conduction behaviour above 80 K for samples with x = 0.01 and 0.08 can be explained using the variable-range hopping and thermally activated mechanism, respectively. Comparative experiments showed that boron bronze phases cannot be obtained by the microwave heating of pure WO₃ powder or a mixture of B₂O₃ and WO₃ under the same conditions.     

Soft chemistry synthesis and crystal structure of MgxCu3−xV2O6(OH)4·2H2O

Mg_xCu_3−xV₂O₆(OH)₄·2H₂O (x ∼ 1), with similar crystal structure as volborthite Cu₃V₂O₇(OH)₂·2H₂O, was successfully prepared by a soft chemistry technique. The method consists of mixing magnesium nitrate and copper nitrate with a boiling solution of vanadium oxide (obtained by reacting V₂O₅ with few mL of 30 vol.% H₂O₂ followed by addition of distilled water). When ammonium hydroxide NH₄OH 10% was added (pH 7.8), a green yellowish precipitate was obtained. Using X-ray powder diffraction data, its crystal structure has been determined by Rietveld refinement. Compared to volborthite, the vanadium coordination changes from tetrahedral VO₄ to trigonal bipyramidal VO₅, and magnesium replaces copper, preferably, in the less distorted octahedron. At 300 °C, the phase formed is similar to the high pressure (HP) monoclinic Cu₃V₂O₈ phase. However at higher temperature, 600 °C, the phase obtained is different from known Cu₃V₂O₈ phases.     

Visible-light-driven NaTaO3−xNx catalyst prepared by a hydrothermal process

NaTaO_3−xN_x catalyst has been successfully synthesized from N-doped Ta₂O₅ precursors by a simple hydrothermal process. The as-prepared samples were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, and diffuse reflectance spectroscopy. Density functional theory calculations suggested that the valence band of the catalysts was composed of the hybrid O 2p and N 2p orbitals, and the visible-light sensitivity is due to the narrowing of the band gap by mixing N 2p and O 2p states. NaTaO_3−xN_x catalyst could decompose the gaseous formaldehyde under the visible-light irradiation (λ > 400 nm), and its photocatalytic activity depended on N dopant concentration. NaTaO_2.943N_0.047 showed the highest photoactivity for the formaldehyde photodegradation.     

Microstructure and electrical conductivity of LaNi0.6Fe0.4O3 prepared by combustion synthesis routes

The continuing development of new materials suitable for solid oxide fuel cells operating at about 650-800 °C is of great interest in recent days. The present investigation deals with the development of a perovskite composition-LaNi_0.6Fe_0.4O₃ (LNF)-prepared following two combustion synthesis routes: citrate-gel (LNC) and urea (LNU). The powders were sintered over a wide temperature range (900-1400 °C) and sintering behavior for LNC and LNU was compared. The thermal expansion coefficient (TEC), electrical and microstructural characteristics of LNF was thoroughly investigated. Electrical conductivities were found to be one and a half times higher than that of most commonly used cathode material, La(Sr)MnO₃. Moreover, the TEC value of LNF was found to be ≈11.4×10⁻⁶ K⁻¹ at 800 °C. The study opens up a possibility of using LNF as a promising cell component for SOFC.     

(ZnO)3In2O3 fine powder prepared by combustion reaction of nitrates-glycine mixture

Conducting fine powder was obtained in the ZnInO system by combustion of the gel prepared from an aqueous solution of mixed zinc and indium nitrates in the presence of glycine. Glycine worked as a fuel as well as a gelling agent in the combustion under the strong oxidizing power of the nitrates. In spite of the low furnace temperature of 350 °C, the product was (ZnO)₃In₂O₃ which has been obtained above 1260 °C in a solid state reaction of a mixture of ZnO and In₂O₃. The combustion synthesis led to an aggregated fine powder of hexagonal platelets of about 40 nm in diameter. Its compacted mass showed an electrical resistivity of about 700 Ω cm. The agglomeration was improved by dispersing the fine powder in an acetic acid aqueous solution.     

Synthesis and electrical properties of cubic NaxWO3 thin films across the metal-insulator transition

Highly oriented (1 0 0) Na_xWO₃ thin films were fabricated in the composition range 0.1 ≤ x ≤ 0.46 by pulsed laser deposition technique. The films showed transition from metallic to insulating behaviour at a critical composition between x = 0.15 and 0.2. The pseudo-cubic symmetry of Na_xWO₃ thin films across the transition region is desirable for understanding the composition controlled metal-insulator transition in the absence of any structural phase transformation. The electrical transport properties exhibited by these films across the transition regime were investigated. While the resistivity varied as T² at low temperatures in the metallic regime, a variable range hopping conduction was observed for the insulating samples. For metallic compositions, a non-linear dependence of resistivity in temperature was also observed from 300 to 7 K, whose exponent varied with the composition of the film.     

Synthesis and crystal structure of two new oxychalcogenides: Eu5V3S6O7 and La10Se14O

The crystal structure determination of two new oxychalcogenides, namely Eu₅V₃S₆O₇ and La₁₀Se₁₄O, is reported. Eu₅V₃S₆O₇ crystallizes in the orthorhombic symmetry (space group Pmmn) with unit cell parameters (in Å): a=17.463(2), b=3.6732(4), and c=10.007(1). This compound is isotypic with the Ln₅V₃S₆O₇ compounds (Ln=La-Nd), and its structure has been refined to R1=0.0248. Eu atoms, which are nine-coordinated by O and S atoms, are associated to form ribbons that are interconnected by [VS₄O₂] octahedrons. La₁₀Se₁₄O crystallizes in the tetragonal symmetry (space group I4₁/acd) with unit cell parameters (in Å): a=15.926(2), and c=21.061(5). The structure was refined to R1=0.0347. La₁₀Se₁₄O is isostructural with the Pr₁₀X₁₄O compounds (X=S and Se). The only structure difference is observed for one La site that is found split, in connection with a mixed O/Se site filling.     

Phase transformation of lithium tungsten bronzes, LixWO3, at room temperature ambient conditions

Samples of Li_xWO₃ with x = 0.05-0.7 were synthesized at 700 °C for 7 days using appropriate amounts of Li₂WO₄, WO₃ and WO₂ in evacuated sealed silica tubes. The products reveal different phases of perovskite tungsten bronze (PTB). An interesting phenomenon observed for the PTB phases is the gradual change in colours when they are exposed at room temperature ambient conditions (in air). This effect has been investigated using X-ray powder diffraction, infrared absorption and optical reflectivity methods for the powdered samples before and after 30 and 90 days in air. The spectra of the samples with x = 0.25-0.5 are dominated by a peak with maximum around 16,000 cm⁻¹ in the Kubelka Munk spectra which is related to the cubic Li_xWO₃ phase. The peak intensity increases with increasing x. After 30 days of exposure in air this peak disappeared for x < 0.5 samples due to a diffusion of Li from Li_xWO₃. X-ray and IR data show a gradual transformation into the lower symmetric phases (PTB_cubic ⇒ PTB_tetragonal ⇒ PTB_orthorhombic ⇒ PTB_monoclinic). The results suggest that Li is attracted by O₂ to the surface forming Li₂O which further reacts with H₂O and CO₂ in air. The in air altered samples regain their original colour when reheated at 500 °C in vacuum.     

Synthesis, crystal structure and magnetic properties of a new lithium cobalt metaphosphate, LiCo(PO3)3

A new lithium cobalt metaphosphate, LiCo(PO₃)₃, is reported for the first time, which was discovered during the exploratory synthesis in Li-Co-P-O system by solid state reaction. The structure has been refined by powder X-ray Rietveld refinement method (P2₁2₁2₁, a = 8.5398(2) Å, b = 8.6326(2) Å and c = 8.3520(2) Å, Z = 4, R_p = 13.6%, R_wp = 19.4%, R_exp = 17.7%, S = 1.11, χ² = 1.23). It is isostructural with LiM(PO₃)₃ (M = Fe, Cu). It contains (PO₃)¹⁻ chains with the Co atoms localized in the octahedral sites, bridging four neighboring chains. The magnetic susceptibility measurement showed a typical paramagnetic behavior of high spin of Co²⁺, following the Curie-Weiss law in the temperature range of 5-300 K. Unlike the olivine type lithium cobalt phosphate, LiCoPO₄, cyclic voltammetry of LiCo(PO₃)₃ assembled in the coin-type cell showed no electrochemical activity in the voltage region of 1-5 V versus Li/Li⁺.     

Synthesis and crystal structure of Sr10Al6O19: a derivative of the perovskite structure type in the system SrO-Al2O3

Sr₁₀Al₆O₁₉ is monoclinic, space group C12/c1, a=34.5823(21) Å, b=7.8460(6) Å, c=15.7485(9) Å, β=103.68(1)°, V=4151.9(7) Å³, Z=8. The structure has been solved from a single crystal diffraction dataset by direct methods and subsequently refined by a full-matrix least-squares process to a residual index of R(|F|)=0.038 for 2537 observed reflections with I>2σ(I). The compound is an oligoaluminate containing highly puckered [Al₆O₁₉]-groups of corner-sharing tetrahedra; it is the first purely aluminate cluster of this type, but it resembles the [□₆O₁₉]-group recently found in α-Sr₁₀□₆O₁₉. Linkage between the hexamers is provided by 11 crystallographically different strontium atoms located in planes parallel (1 0 0). They are coordinated by six-eight next oxygen neighbours. The structure can be derived from perovskite, ABO₃, by introducing ordered vacancies into the substructure of the oxygen atoms. The A-sites in Sr₁₀Al₆O₁₉ are exclusively occupied by Sr atoms, whereas strontium and aluminum atoms reside on the B-positions in the ratio 1:3. The relationship with perovskite can be expressed in the crystal chemical formula Sr(Al_3/4Sr_1/4)(O_19/8□_5/8).     

Thermal stability against reduction of LaMn1−yCoyO3 perovskites

Thermal and reduction-oxidation stability of substituted LaMn_1−yCo_yO₃ perovskite-type oxides (0.0 ≤ y_Co ≤ 1.0) prepared by the citrate route have been studied by means of surface area, X-ray diffraction, FTIR spectroscopy and magnetic properties. The perovskite orthorhombic structure is found for y_Co ≤ 0.5, with the exception of y_Co = 0.1, which corresponds better to rhombohedral LaMnO_3.15. For y_Co > 0.5 the diffraction profiles are quite similar to the cobaltite’s rhombohedral structure. Magnetic iso-field studies (ZFC-FC) reveal that, for y_Co ≤ 0.50, the system presents an antiferromagnetic canted-like ordering of the Mn/Co sublattice, in which the presence of divalent Co ion creates Mn³⁺-Mn⁴⁺ pairs that interact ferromagnetically through the oxygen orbital. This interpretation is confirmed by the magnetization loops, in which the magnetic moment increases when substituting Mn for Co. Therefore, the general trend is: for y_Co ≤ 0.5, the Co ions are inserted in the manganite structure and for y_Co > 0.5, the Mn ions are inserted in cobaltite structure. The enhancement of the ferromagnetic properties and the thermal stability against reduction for y_Co = 0.5 is attributed to optimized Co²⁺-Mn⁴⁺ interactions.     

Influence of fuels on the morphology of undoped Y3Al5O12 and photoluminescence of Y3Al5O12:Eu prepared by a combustion method

Undoped and Eu-doped yttrium aluminum garnet nano-powders were prepared by a facile combustion method with citric acid/ethylene diamine tetraacetic acid (EDTA) as fuels and nitrates as oxidizers. The precursors and powders calcined at 1030 °C were investigated using thermogravimetric (TG), differential thermal analysis (DTA), X-ray diffraction (XRD), scanning electron microscope (SEM), and Brunauer-Emmett-Teller (BET) surface area measurements. It was found that the powders could be indexed with a garnet structure. The grains were in shape of hemispherical with sizes between 60 nm and 100 nm. With decreasing the citric acid/EDTA ratio, the crystallite size decreased steadily and the specific surface area increased. Investigations of photoluminescence (PL) revealed that as-synthesized YAG:Eu³⁺ phosphor samples exhibited an orange emission band with a main peak at 591 nm under the excitation of 394 nm. As citric acid amounts increased, the quality of crystallinity became higher and the luminescent properties were monotonously enhanced.     

Crystal structure and properties of the new complex vanadium oxide K2SrV3O9

The new complex vanadium oxide K₂SrV₃O₉ has been synthesized and investigated by means of X-ray powder diffraction (XPD), electron microscopy and magnetic susceptibility measurements. The oxide has an orthorhombic unit cell with lattice parameters a = 10.1922(2) Å, b = 5.4171(1) Å, c = 16.1425(3) Å, space group Pnma and Z = 4. The crystal structure of K₂SrV₃O₉ has been refined by Rietveld method using X-ray powder diffraction data. The structure contains infinite chains built by V⁴⁺O₅ square pyramids linked to each other via VO₄ tetrahedra. The chains form layers and potassium and strontium cations orderly occupy structural interstices between these layers. Electron diffraction as well as high resolution electron microscopy confirmed the structure solution. Magnetic susceptibility measurements revealed an antiferromagnetic interaction with J of the order of 100 K inside the chains and no long-range magnetic order above 2 K. The origin of the magnetic exchange is likely a result of super-exchange interaction through the two VO₄ tetrahedra linking the polyhedra with the magnetic V⁴⁺ cations.     

New cathode compositions based on La0.84Sr0.16Mn1−xMxO3, where M = Al, Ga for solid oxide fuel cell

In order to identify new cathode compositions for the high temperature solid oxide fuel cell, we have investigated the effect of the trivalent cations Al and Ga at the Mn site of the well-studied cathode composition La_0.84Sr_0.16MnO₃. All the compositions have been prepared by the low temperature citrate-nitrate auto-ignition process and sintered within the temperature range of 1150-1350 °C for 4 h. In order to understand the compatibility of the prepared samples as alternative cathode materials, we compared their electrical conductivity and thermal expansion coefficient with those of La_0.84Sr_0.16MnO₃ and yttria-stabilized zirconia. A 10 mol% Al doped La_0.84Sr_0.16MnO₃ composition exhibited a conductivity of around 122 S cm⁻¹ at 950 °C and a thermal expansion coefficient of 11.04 × 10⁻⁶ K with a minimum reactivity towards yttria-stabilized zirconia. Though the conductivity of the new composition is lower than that of La_0.84Sr_0.16MnO₃ (169 S cm⁻¹ at 950 °C), it is still high enough for use as a cathode material.     

Synthesis, structural and magnetic properties of La1−xCdxFeO3 (0.0 ≤ x ≤ 0.3) orthoferrites

Nanocrystalline La_1−xCd_xFeO₃ (0.0 ≤ x ≤ 0.3) solid solutions have been synthesized by a single-step solution combustion method at a relatively low temperature of 400 °C. The combustion-synthesized solid solutions were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), and magnetic measurements. The crystal structure examined by XRD indicates that the samples were single-phase, and crystallize in an orthorhombic (space group, Pbnm no. 62) structure. The parent and doped compounds showed canted antiferromagnetic behavior associated with an increase in magnetic moment with Cd doping. The changes in magnetic properties of the materials are correlated to the changes in structural features resulting from the Rietveld structural refinement of the materials.     

Ba3ZnTa2−xNbxO9 and Ba3MgTa2−xNbxO9 (0≤x≤1): synthesis, structure and dielectric properties

Oxides belonging to the families Ba₃ZnTa_2−xNb_xO₉ and Ba₃MgTa_2−xNb_xO₉ were synthesized by the solid state reaction route. Sintering temperatures of 1300°C led to oxides with disordered (cubic) perovskite structure. However, on sintering at 1425°C hexagonally ordered structures were obtained for Ba₃MgTa_2−xNb_xO₉ over the entire range (0≤x≤1) of composition, while for Ba₃ZnTa_2−xNb_xO₉ the ordered structure exists in a limited range (0≤x≤0.5). The dielectric constant is close to 30 for the Ba₃ZnTa_2−xNb_xO₉ family of oxides while the Mg analogues have lower dielectric constant of ∼18 in the range 50 Hz to 500 kHz. At microwave frequencies (5-7 GHz) dielectric constant increases with increase in niobium concentration (22-26) for Ba₃ZnTa_2−xNb_xO₉; for Ba₃MgTa_2−xNb_xO₉ it varies between 12 and 14. The “Zn” compounds have much higher quality factors and lower temperature coefficient of resonant frequency compared to the “Mg” analogues.     

Metallization of La1/3NbO3 by lithium incorporation

Lithium ion was successfully introduced into La_1/3NbO₃ with an A-site-deficient perovskite-type structure. The crystal structure and transport properties of La_1/3Li_xNbO₃ were investigated as a function of Li content (x = 0-0.59). The lattice parameters of La_1/3Li_xNbO₃ with an orthorhombic cell were enlarged with increasing Li content for x ≤ 0.3, and the structure was transformed to a pseudo-tetragonal cell for x = 0.44. The temperature dependence of electrical resistivity gradually changed from insulating to metallic with increasing x, and thermoelectric power measurement indicated that the carriers were electrons. In X-ray photoelectron spectra of the incorporated samples, Nb_3d⁴⁺ peaks appeared in addition to Nb_3d⁵⁺ peaks, which was consistent with the change of the transport properties. In spite of the success of metallization, no diamagnetic signal indicative of supercondcutivity was observed in La_1/3Li_0.59NbO₃ down to 1.8 K.     

Synthesis of highly dispersed MnCeOx catalysts via a novel “redox-precipitation” route

A new synthesis route driving redox-precipitation reactions among Mn^VII, Ce^III and Mn^II precursors in basic aqueous solution yields MnCeO_x catalysts (Mn loading, 9-33 wt%) with improved textural and structural properties in comparison to the conventional co-precipitation technique. Irrespective of the Mn loading, BET, X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) findings prove that the new method ensures a very high reproducibility in all the main physico-chemical properties of MnCeO_x catalysts. Enabling a monolayer dispersion of the active phase, the “redox-precipitation” method greatly promotes the reducibility and the surface affinity of the MnCeO_x system towards gas-phase oxygen.     

Synthesis and thermal stability of W-doped VO2 nanocrystals

Pure and W-doped vanadium dioxide nanocrystals have been synthesized by using V₂O₅ and oxalic acid as precursors via a thermolysis method. The VO₂ nanocrystals have a nearly spherical morphology with size ranging from 50 to 100 nm. The metal-insulator transition (MIT) temperature of the nanocrystals decreases with increasing W-doping content. The successive heat-induced fatigue character of the MIT in W-doped VO₂ nanocrystals was investigated by DSC analysis together with structural study, and a high stability upon heating–cooling cycles was found with respect to MIT temperature, peak temperature and latent heat of the phase transition.     

R3Mn1.5CuV0.5O9 (R = Y, Ho, Er, Tm, Yb and Lu) and Lu3Mn3−3xCu2xVxO9: New noncentrosymmetric oxides related to YMnO3

We report formation of new noncentrosymmetric oxides of the formula, R₃Mn_1.5CuV_0.5O₉ for R = Y, Ho, Er, Tm, Yb and Lu, possessing the hexagonal RMnO₃ (space group P6₃cm) structure. These oxides could be regarded as the x = 0.5 members of a general series R₃Mn_3−3xCu_2xV_xO₉. Investigation of the Lu-Mn-Cu-V-O system reveals the existence of isostructural solid solution series, Lu₃Mn_3−3xCu_2xV_xO₉ for 0 < x ≤ 0.75. Magnetic and dielectric properties of the oxides are consistent with a random distribution of Mn³⁺, Cu²⁺ and V⁵⁺ atoms that preserve the noncentrosymmetric RMnO₃ structure.