Isomorphic substitution of neodymium and gadolinium for calcium in synthetic hydroxovanadate

Isomorphic substitution of neodymium and gadolinium for calcium in synthetic hydroxovanadate Ca_{5 ? x} M _x (VO₄)₃(OH)_{1 ? x} O _x (M = Nd, Gd) is studied in the range 700–1000°C using X-ray powder diffraction, single-crystal X-ray diffraction (Rietveld technique), and IR spectroscopy. Single-phase solid solutions at 800°C are formed with x ≤ 0.35 for M(III) = Nd and x ≤ 0.3 for M(III) = Gd. With high x, the apatite solid solution coexists with Ca₃(VO₄)₂, Nd₂O₃, and X phases. With increasing x in the homogeneous region, the intensity of the bands of stretching vibrations and librations of OH groups decrease. Single-crystal X-ray diffraction shows that neodymium and gadolinium substitute for calcium in solid solutions mostly in Ca(2) positions.     

Oxygen Nonstoichiometry and Transport Properties of Mixed-Conducting Ce<Subscript>0.6–<Emphasis Type="Italic">x</Emphasis></Subscript>La<Subscript>0.4</Subscript>Pr<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>2–δ</Subscript>

The oxygen nonstoichiometry and electrical conductivity of fluorite-type solid solutions Ce_0.6?xLa_0.4Pr _x O_2–δ (x = 0.1–0.2) were studied in the oxygen partial pressure range 10^–19–0.35 atm at 1023–1223 K. It was confirmed that the Pr^4+/3+ and Ce^4+/3+ redox pairs, which determine the concentration of p- and n-type electron charge carriers, play the dominant roles under oxidizing and reducing conditions, respectively. The conductivity vs. charge carrier concentration dependencies in these conditions are almost linear. Increasing praseodymium content leads to a substantially higher hole conductivity and an expanded range of the oxygen nonstoichiometry variations at high oxygen partial pressures. Under reducing conditions when praseodymium cations become trivalent opposite trends are observed on doping.     

Modification of mixed conducting Ba<Subscript>0.5</Subscript>Sr<Subscript>0.5</Subscript>Co<Subscript>0.8</Subscript>Fe<Subscript>0.2</Subscript>O<Subscript>3–δ</Subscript> by partial substitution of cobalt with tungsten

The Ba_0.5Sr_0.5Co_0.8–xW_xFe_0.2O_3–δ (х = 0–0.1) materials prepaMIECred by partial substitution of cobalt in BSCF with tungsten were studied. The tungsten solubility limit in the structure of cubic perovskite BSCF was shown to be ~2%. The doping with the highly charged W⁶⁺ (2%) cation improved the functional properties of BSCF: it increased the oxygen permeability and membrane stability in the CO₂-containing atmosphere and suppressed the cubic–hexagonal perovskite polymorphic transition. This stabilizes high oxygen fluxes during long-term stability tests.     

Effects of base composition and dopants on the properties of hexagonal ferrites

The effects of the base composition and dopants on the saturation magnetization and coercivity of hexaferrites BaAl_xFe_12–xO₁₉, SrAl_xFe_12–xO₁₉, BaGa_xFe_12–xO₁₉, SrGa_xFe_12–xO₁₉, BaSc_xFe_12–xO₁₉ and SrSc_xFe_12–xO₁₉ have been studied. Isomorphic substitutions of Al₂O₃, Ga₂O₃, and Sc₂O₃ for Fe₂O₃ in barium and strontium ferrites are found to increase coercivity due to increasing crystallographic anisotropy constant and to reduce the saturation magnetization value. Processes controlling microstructure formation, specifically recrystallization processes, are shown to have a noticeable effect on the level of properties of the ferrites under study with the use of dopants. The most efficient dopants are boron, calcium, and silicon oxides, which provide the formation of relatively fine-grained structures. The increased coercivity upon doping with these dopants is also due to the formation of grain-boundary interlayers of a nonmagnetic glassy phase and the associated efficient retardation of moving domain walls.     

Ceramic and Transport Characteristics of Electrolytes Based on Mg-Doped LaYO<Subscript>3</Subscript>

Effect of magnesium on the sinterability, phase composition, microstructure, and transport properties of proton-conducting materials of composition LaY_1–xMg_xO_3–δ (х = 0, 0.05, 0.1) was studied. Ceramic samples were obtained by using the citrate-nitrate synthesis method at various sintering temperatures (1250–1400°C). It was shown that, for the samples with x = 0.05 and 0.1, the relative density was no less than 95% at a sintering temperature of 1350°C, whereas undoped lanthanum nitrate has this density at 1450°C. An X-ray diffraction analysis and scanning electron microscopy demonstrated that introduction of a small amount of magnesium (x = 0.05) is sufficient for forming the single-phase and high-dense ceramics. Electrical conductivity data show that the LaY_0.95Mg_0.05O_3–δ sample has high overall and ionic conductivities.     

Preparation,structure, and charge transport characteristics of BIFEVOX ultrafine powders

Existence boundaries, structure, and transport parameters of ultrafine powders were studied in Bi₄V_{2 ? x} Fe _x O_{11 ? x} (BIFEVOX) solid solutions. The details of synthesis of the solid solutions via liquid precursors are analyzed comparatively. In general, BIFEVOX formation via liquid precursors is similar to phase formation in solid-phase synthesis. With low iron levels (x = 0.05–0.1), solid solutions are formed in the monoclinic α phase (space group C2/m) The compositions with x = 0.125 and 0.15 are mixtures of α- and β phases. In the range 0.2 < x < 0.7, the Bi₄V_{2 ? x} Fe _x O_{11 ? x} solid solution has the structure of the γ phase of Bi₄V₂O₁₁ (space group I4/mmm). The β phase in the system in question has a very narrow existence range in the vicinity of x = 0.175. The average particle sizes of the powders prepared by various methods are within 0.5–3 μm. In the powders prepared via liquid precursors, however, the distribution peak shifts toward smaller sizes, to 0.3–1 μm. Mechanical activation conserves the structure of the γ phase of BIFEVOX, and unit cell parameters change only insignificantly; however, the crystal lattice is slightly distorted. The electrical conductivity of BIFEVOX was studied as a function of temperature, preparation technology, and composition using impedance spectroscopy. Equivalent circuits of cells were analyzed. The conductivity of samples prepared by solution technology is always higher than for samples prepared by the solid-phase process. Features of electrical conductivity versus temperature for various phases are noted. All transitions on the conductivity curves match the features of linear thermal expansion curves. Compositions with doping levels x= 0.1–0.3 have the highest total conductivities.     

Specific features of phase equilibriums in Ln–Ba–Fe–O systems

Formation of five-layered Ln_2–εBa_3+εFe₅O_15–δ phases [exhibiting nanoscale ordering with layer-by-layer location of the cations in the Ln–Ba–(Ln,Ba)–(Ln,Ba)–Ba–Ln perovskite-type structure] has occurred in the Ln–Ba–Fe–O (Ln = Y, Pr, Nd, Sm, Eu, and Gd) systems at 1100°С in air. Partial substitution of iron with cobalt (Ln_2–εBa_3+εFe_5–yCo_yO_15–δ, Ln = Nd, Sm, Eu) has stabilized formation of the ordered structure. The oxygen content in the complex oxides has been determined in air over a wide temperature range by means of high-temperature thermogravimetry and iodometric titration. The change in oxygen content with temperature for the phases with five-layered ordering was significantly smaller than for the disordered phases.     

Electrophysical properties of bismuth titanates with the pyrochlore structure Bi<Subscript>1.6</Subscript>M<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Ti<Subscript>2</Subscript>O<Subscript>7–δ</Subscript> (M = In,Li)

Lithium-containing bismuth titanates with the pyrochlore-type structure Bi_1.6Li_xTi₂O_7–δ were obtained for the first time. The formation of the pyrochlore phase was confirmed by X-ray diffraction analysis, scanning electron microscopy and local microanalysis. In Bi_1.6M_xTi₂O_7–δ, the lithium and indium are occupied the bismuth sites, primarily. The electrophysical properties of doped bismuth titanates were studied by impedance spectroscopy in the frequency range 1–10⁶ Hz. In the low-temperature range (of up to ~400°C), electron conductivity predominates; above 400°C, the oxygen-ion type of conductivity is revealed. In the range p(O₂) = 0.21–1 atm, the average value of the sum of ion transport numbers is 0.5 at 500–550°C. The relaxation process was found from the frequency dependences of the dielectric parameters (ε', tan δ, M''), which was of the same type for systems with different dopants (In, Li) probably due to the hopping mechanism of oxygen conductivity.     

The oxygen nonstoichiometry,defect structure,and thermodynamic characteristics of disordering of nickel-and iron-substituted lanthanum cobaltites

The oxygen nonstoichiometry of nickel-and iron-substituted lanthanum cobaltites of the compositions LaCo_1?x Ni _x O_3?δ (x = 0.1, 0.3) and LaCo_0.9Fe_0.1O_3?δ was studied by high-temperature thermogravimetric analysis over the temperature and oxygen partial pressure ranges 1223–1473 K and 10^?3–0.21 atm. The partial replacement of cobalt with nickel (an acceptor impurity) in lanthanum cobaltite was found to increase the number of defects in the oxygen sublattice, whereas the replacement with iron (a donor impurity) decreased this number. Correlations between the experimental \(\log p_{O_2 } = f(\delta )\) dependences and the suggested models of formation of point defects were analyzed taking into account the formation of Schottky defects. Interrelation between the defect structure, partial molar thermodynamic characteristics of oxygen release from the crystal lattices of the oxides studied, and the nature of substituting impurities (Ni and Fe) in lanthanum cobaltite was demonstrated.     

Phase equilibria involving solid solutions in the Li–Mn–O system

Phase equilibria involving LiMn₂O_4-, Li₂MnO_3-, LiMnO_2-, Mn₃O_4-, and MnO-base solid solutions were studied with varied temperature and partial oxygen pressure. The \({P_{{o_2}}}\)–T and x–y projections of the P–T–x–y phase diagram of the Li–Mn?O system were constructed, as well as the key x–y isotherms of the Li₂O–MnO–MnO₂ quasi-ternary system. In some experiments, the authors’ hydride lithiation method was employed to prepare lithium-rich homogeneous three-component nonstoichiometric phases.     

Effect of phosphate doping on electric properties and chemical stability of Ba<Subscript>4</Subscript>Ca<Subscript>2</Subscript>Nb<Subscript>2</Subscript>O<Subscript>11</Subscript> protonic conductor

Conductivity of perovskite phosphate–substituted solid solutions of Ba₄Ca₂Nb_{2 –x} P _x O₁₁ (0.0 ≤ x ≤ 0.5) was studied as a function of temperature, partial pressure of oxygen and water vapors. It is proved that the studied systems are protonic conductors at the temperatures below 600°C in the atmosphere with elevated content of water vapors (pH₂O = 1.92 × 10^–2 atm). Introduction of the tetrahedral [PO₄] group in the complex oxide matrix of Ba₄Ca₂Nb₂O₁₁ results in an increase in the oxygen–ionic (dry air, pH₂O = 1.91 × 10^–4 atm) and protonic conductivities (wet air, pH₂O = 1.92 × 10^–2 atm). Is it found that the doping causes a considerable increase in chemical stability of phases with respect to carbon dioxide.     

Crystal structure and conduction of BICUTIVOX

Existence boundaries, structure, and transport parameters were studied for Bi₄V_{2 ? x} Cu _x/2Ti _x/2O_{11 ? x} solid solutions. Doping levels within x = 0.025–0.15 distort the C2/m crystal lattice (this lattice is characteristic of individual the Bi₄V₂O₁₁ phase) and lowers its symmetry to triclinic. The solid solutions with 0.25 ≤ x ≤ 0.30 crystallize in tetragonal space group I4/mmm. High-temperature X-ray diffraction and dilatometry measurements for Bi₄V_{2 ? x} Cu _x/2Ti _x/2O_{11 ? x} (x ≤ 0.35) solid solutions verified the existence of three structural varieties within 298–1023 K. Electrical conductivity of BICUTIVOX was studied by impedance spectroscopy as a function of temperature, composition, and oxygen partial pressure. Equivalent circuits of cells were analyzed. Features of electrical conductivity versus temperature for the structural varieties are noted. Above 873 K, the solid solutions samples with x = 0.05 have the highest conductivity. At lower temperatures, higher conductivities are in the solid solutions that retain the γ phase in the low-temperature region. The dominant oxygen-ion conduction mechanism was discovered in the solid solutions.     

Synthesis,structure, and properties of substituted bismuth niobates Bi<Subscript>3</Subscript>Nb<Subscript>1–<Emphasis Type="Italic">x</Emphasis></Subscript>Er<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>7–δ</Subscript>

Results are reported of a study of the structural and electrical characteristics of substituted bismuth niobates with composition Bi₃Nb_1–x Er _x O_7–δ, which are promising oxygen-ion conductors. The homogeneity regions of solid solutions were determined by X-ray phase analysis and electron microscopy with X-ray fluorescence microanalysis, and their crystal-chemical parameters were calculated. The electrical conductivity of sintered samples was examined by impedance spectroscopy.     

Electrical Conductivity,Thermal Expansion and Electrochemical Properties of Perovskites PrBaFe<Subscript>2–<Emphasis Type="Italic">x</Emphasis></Subscript>Ni<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>5 + δ</Subscript>

In order to evaluate applicability of mixed-conducting PrBaFe_2–xNi _x О_{5 + δ} perovskites for cathodes of solid oxide fuel cells (SOFCs), their crystal structure, thermal and chemical expansion, electrical conductivity and electrochemical behavior were studied. The solubility limit of nickel in PrBaFe₂O_{5 + δ} corresponds to x = 0.8. At x > 0.2, the disordered cubic phase transformed into the tetragonal phase. The maximum level of conductivity (50–120 S/cm) at the operating temperatures of SOFC was found for the composition with the maximum nickel content, PrBaFe_1.2Ni_0.8О_{5 + δ}. This material is also characterized by moderate thermal and chemical expansion relative to other ferrite-nickelates. The polarization resistance of a porous PrBaFe_1.2Ni_0.8О_{5 + δ} cathode in a cell with a protective Ce_0.6La_0.4O_2–δ layer and a solid electrolyte (La_0.9Sr_0.1)_0.98Ga_0.8Mg_0.2O_3–δ was ~0.9 Ohm cm² at a temperature of 1073 K, atmospheric oxygen pressure, and current density of–120 mA cm^–2.     

Synthesis,structure, and conduction of solid solutions BIMEVOX (Me = Cu,Ti)

Conditions for synthesizing single-phase solid solutions Bi₄V_{2 ? x} Cu _x/2Ti _x/2O_{11 ? x} and Bi_{4 ? x/2}V_{2 ? x/2}Cu _x/2Ti _x/2O_{11 ? x/2} are studied. The sequence of phase transformations is determined. Possible domains of stability of polymorphic modifications and the overall conductivity as a function of temperature and composition are studied. The structure of the γ-modification is refined using Rietveld’s full-profile analysis.     

High-pressure defect phase Tm<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Cu<Subscript>3</Subscript>V<Subscript>4</Subscript>O<Subscript>12</Subscript>

Perovskite-related oxide Tm _x Cu₃V₄O₁₂ (space group Im \(\bar 3\), Z = 2, a = 7.262?7.273 Å) with vacancies in the cationic sublattice has been prepared for the first time under barothermal conditions (p = 7.0?9.0 GPa, T = 900?1100°C). Electric resistivity (10–300 K) and magnetic susceptibility (0–300 K) were studied as a function of temperature. Tm _x Cu₃V₄O₁₂ is shown to have a metallic conductivity and paramagnetism.     

Transport and Electrochemical Properties of SrFe(Al,Mo)O<Subscript>3–δ</Subscript>

In this work, effects of molybdenum doping on the crystal structure, stability, electrical conductivity, oxygen permeability and thermomechanical properties of Sr(Fe,Al)O_3–δ-based perovskites, were studied. The electrochemical performance of model anodes of solid oxide fuel cells (SOFCs), made of SrFe_0.7Mo_0.3O_3–δ, was assessed. Whilst the introduction of Mo cations improves structural stability with respect to the oxygen vacancy ordering processes, excessive molybdenum content leads to a worse phase and mechanical stability under oxidizing conditions. Mo-doping was shown to decrease the thermal and chemical expansivity, to reduce p-type electronic conductivity and to increase n-type electronic conduction. The oxygen permeation fluxes through gas-tight Sr_0.97Fe_0.75Al_0.2Mo_0.05O_3–δ membranes are determined by both the bulk oxygen diffusion and surface exchange kinetics. The role of the latter factor increases on decreasing temperature and reducing oxygen partial pressure. Due to a relatively high electrical conductivity and moderate thermal expansion coefficients in reducing conditions, SrFe_0.7Mo_0.3O_3–δ-based anodes show a substantially high electrochemical activity.     

Iridium–nickel composite oxide catalysts for oxygen evolution reaction in acidic water electrolysis

A series of Ir_1–xNi_xO_2–y (0 ≤ x ≤ 0.5) composite oxides have been prepared by a simple pyrolysis method in ethanol system and used as the electrocatalysts for OER in acidic medium. The materials have been characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF) and scanning electron microscopy (SEM). The electrochemical performances of these Ir_1–xNi_xO_2–y composite catalysts are evaluated by cyclic voltammetry (CV) and steady-state measurements. The resulting oxides with the Ni content (x) less than 0.3 have a complex nature of metal Ir and rutile structure IrO₂ which is similar to the Ir oxide prepared by the same approach and possess the contracted lattice resulted from the Ni-doping. Although the addition of Ni reduces the electroactive surface areas due to the coalescence of particles, the catalytic activity of the Ir_1–xNi_xO_2–y (0 < x ≤ 0.3) catalysts is slightly higher than that of the pyrolyzed Ir oxide. Regardless of the surface area difference, the intrinsic activity first increases and then decreases with the Ni content in Ir_1–xNi_xO_2–y catalysts, and the intrinsic activity of Ir_0.7Ni_0.3O_2–y catalyst is about 1.4 times of the Ni-free Ir oxide mainly attributed to the enhancement of conductivity and a change of the binding energy as increasing amount of the incorporated Ni with respect to the pure IrO₂. The Ir_0.7Ni_0.3O_2–y catalyst shows a prospect of iridium-nickel oxide materials in reducing the demand of the expensive Ir oxide catalyst for OER in acidic water electrolysis.     

High-pressure defect phase Nd<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Cu<Subscript>3</Subscript>V<Subscript>4</Subscript>O<Subscript>12</Subscript>

A perovskite-like oxide Nd _x Cu₃V₄O₁₂ (space group Im \(\bar 3\) Z = 2, a = 7.278–7.322 Å) with cationic vacancies was prepared for the first time under triaxial compression of p = 6.0–9.0 GPa at 700–1300°C. The compound has a metal-type conductivity, paramagnetic properties, and a phase transition.     

Chemical composition-structure-properties relations in a series of Sr<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Ba<Subscript>1-<Emphasis Type="Italic">x</Emphasis></Subscript>Nb<Subscript>2</Subscript>O<Subscript>6</Subscript> compounds

Based on structural studies of Sr _x Ba_1-x Nb₂O₆ crystals with different concentrations of strontium and barium, the structural causality of optical nonlinearity of these crystalline materials is established. YAG:Nd laser radiation of the crystals results in a monotonic decrease in the second harmonic intensity with increasing strontium concentration in a sample. Fine details of the structure responsible for this effect are determined.