Synthesis,morphology, and activity of La<Subscript>1–x</Subscript>Ag<Subscript>x</Subscript>MnO<Subscript>3 ± y</Subscript> catalysts

La_1–xAg_xMnO_{3 ± y} (x = 0-0.3) mixed oxides have been synthesized by the pyrolysis of polymer–salt compositions using different organic compounds and different salt: organic compound ratios. The correlation between the reaction medium temperature during pyrolysis, the composition of the resulting oxide, and synthesis conditions has been investigated. The effect of these conditions on the character of the pyrolysis process, on the phase composition and microstructure of the resulting oxide particles and metallic silver, and on their mutual distribution is reported. The catalytic properties of the synthesized oxides in methane and soot oxidation are considered, and a correlation is established between the catalytic activity of the oxides and the synthesis conditions.     

Phase equilibria,charge transport,and mass transport in Sr<Subscript>4</Subscript>Nb<Subscript>2</Subscript>O<Subscript>9</Subscript>-“M<Subscript>4</Subscript>Nb<Subscript>2</Subscript>O<Subscript>9</Subscript>” (M = Cd,Cu, Ni,and Zn) systems

Homogeneous fields of Sr_{4 − x} M _x Nb₂O₉ (M = Cd, Cu, Ni, or Zn) solid solutions were determined using powder X-ray diffraction. Phase fields were plotted proceeding from the tolerance factor t and electronegativity ratio $ \bar k_A /\bar k_B $ \bar k_A /\bar k_B with a satisfactory fit of experimental results. Thermogravimetry was used to establish the major kinetic laws of solid-phase synthesis (conversion, rate-controlling stage, and effective activation energy) in (4 − x)SrCO₃ + xMO + Nb₂O₅ powdery mixtures. Direct radiometry was used to determine ⁹⁰Sr, ⁶³Ni, and ⁶⁵Zn self-diffusion coefficients in solid solutions based on the Sr₄Nb₂O₉ phase. Electrical conductivity was measured as a function of temperature for all Sr₄Nb₂O₉-“M₄Nb₂O₉” samples. The conductivity of Sr_{4 − x} M _x Nb₂O₉ (M = Cd, Cu, Ni, or Zn) solid solutions has a mixed ion-electron character.     

Synthesis,microstructure, and electric properties of CaZr<Subscript>0.9</Subscript>Y<Subscript>0.1</Subscript>O<Subscript>3 – δ</Subscript> films obtained on porous SrTi<Subscript>0.8</Subscript>Fe<Subscript>0.2</Subscript>O<Subscript>3 – δ</Subscript> supports

Compact CaZr_0.9Y_0.1O_3–δ (CZY) film on a porous SrTi_0.8Fe_0.2O_3–δ (STF) support is obtained using the technique of deposition from solutions of inorganic salts in ethanol. According to the data of scanning electron microscopy (SEM), the film has a nanoporous granular structure with the grain size of 0.2 to 1 μm. The thickness of the CZY film on the STF support is about 3 μm after 15-fold solution application. The results of studying the elemental composition showed that elements of the support diffuse into the film in the course of synthesis. Analysis of the data of impedance spectroscopy shows that conductivity of the CZY film is limited the grain bulk. It is assumed that the comparatively low conductivity activation energy of the film (50.3 kJ/mol) is due to diffusion of elements of the STF support that results in variation of the film composition and properties.     

Synthesis and physicochemical study of M<Subscript>4</Subscript>Na<Subscript>2</Subscript>V<Subscript>10</Subscript>O<Subscript>28</Subscript> · 10H<Subscript>2</Subscript>O (M=K,Rb, NH<Subscript>4</Subscript>)

The formation conditions and physicochemical properties of binary decavanadates M₄Na₂V₁₀O₂₈ · 10H₂O (M=K, Rb, NH₄), synthesized by crystallization from saturated solutions of the NaVO₃-MH₂AsO₄-H₂O systems, were studied by chemical analysis, X-ray powder diffraction, microscopy, thermogravimetry, and IR spectroscopy. To optimize the synthesis conditions of M₄Na₂V₁₀O₂₈ · 10H₂O, the ( 1-x)NaVO₃ · 2H₂O · xMH2AsO4-H₂O (0.2 ≤ x ≤ 0.8) isomolar series method was applied to studying the interaction in the NaVO₃-MH₂AsO₄-H₂O systems (M = K, Rb, Cs) at the 0.4 mol/L total molar concentration of NaVO₃ and MH₂AsO₄ in solutions. The studied M₄Na₂V₁₀O₂₈ · 10H₂O compounds were shown to be isostructural with triclinic crystals (Z= 1, space group P $ \bar 1 $ \bar 1 ), and their unit cell parameters were estimated.     

Solid solutions (Ru,Nb)Sr<Subscript>2</Subscript>(Sm<Subscript>1.4</Subscript>Ce<Subscript>0.6</Subscript>)Cu<Subscript>2</Subscript>O<Subscript>10−δ</Subscript>: Synthesis,structure, and properties

Solid solutions of as-batch composition (Ru_1?x Nb _x )Sr₂(Sm_1.4Ce_0.6)Cu₂O_10?δ (the Ru,Nb)-1222 phase), where x = 0.0, 0.25, 0.50, 0.75, or 1.00, have been synthesized and characterized by X-ray diffraction. A correlation is proposed between the refined composition of the Ru-1222 and Nb-1222 phases and their structural features. With increasing oxygen concentration in the Ru-1222 phase, the superconducting transition temperature increases from T _c = 28 to T _c = 34 K. The composition and magnetic properties of the Ru-1222 phase are affected by the batch composition: unlike in Ru + RuO₂ mixtures, the presence of ruthenium in the batch decreases the oxygen proportion and increases the magnetic ordering temperature T _m; the phase of as-batch composition NbSr₂(Sm_1.4Ce_0.6)Cu₂O_10?δ is paramagnetic.     

Theoretical analysis of the system Li,K, Ca,Ba||F,WO<Subscript>4</Subscript>: Physicochemical properties of the system LiF–K<Subscript>2</Subscript>WO<Subscript>4</Subscript>–BaF<Subscript>2</Subscript>–CaF<Subscript>2</Subscript>–BaWO<Subscript>4</Subscript>

The differentiation of the quaternary reciprocal system Li, K, Ca, Ba||F, WO₄ was performed based on the graph theory using special software. Stable and metastable complexes of the system were found using a matrix of reciprocal pairs of salts. For the first time, by a set of physicochemical analysis methods (differential thermal, visual polythermal, and X-ray powder diffraction analyses), based on the method of thermal analysis of successive projections of the composition polytope, the quaternary system LiF–K₂WO₄–CaF₂–BaF₂–BaWO₄, which is a stable complex of the quaternary reciprocal system Li, K, Ca, Ba||F, WO₄, was studied and the coordinates of invariant points were determined.     

Stable tetrahedron LiF–KI–K<Subscript>2</Subscript>CrO<Subscript>4</Subscript>–Li<Subscript>2</Subscript>CrO<Subscript>4</Subscript> of the quaternary reciprocal system Li,K||F,I, CrO<Subscript>4</Subscript>

The stable tetrahedron LiF–KI–K₂CrO₄–Li₂CrO₄ of the quaternary reciprocal system Li, K||F, I, CrO₄ was experimentally studied by differential thermal analysis. The compositions and melting points of mixtures of components at two eutectic points were determined. Based on experimental data, a T–x–y–z model of the phase complex was constructed, which allows one to solve problems of building polythermal and isothermal sections. A method for constructing the diagram of material balance of equilibrium phases for a given composition was developed. The diagram enables one to find the ratio between the amounts of the liquid and solid phases at constant temperature and also monitor the change in the composition of the phases within a chosen temperature range.     

Cutting Tetrahedron LiVO<Subscript>3</Subscript>–KBr–KVO<Subscript>3</Subscript>–LiKMoO<Subscript>4</Subscript> of the Quinary Reciprocal System Li,K||F,Br, VO<Subscript>3</Subscript>, MoO<Subscript>4</Subscript>

The cutting tetrahedron LiVO₃–KBr–KVO₃–LiKMoO₄ of the quinary reciprocal system Li, K||F, Br, VO₃, MoO₄ was studied by differential thermal analysis. The composition and melting point of the alloy corresponding to a quaternary eutectic were determined (11.3 mol % LiVO₃, 18.0 mol % KBr, 57.0 mol % KVO₃, 13.7 mol % Li₂MoO₄ + K₂MoO₄, 318°С).     

Sol–Gel Synthesis of Na<Subscript>2</Subscript>O-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-P<Subscript>2</Subscript>O<Subscript>5</Subscript> Glasses and their Characterization by NMR,SNMS, and AFM

Sodium aluminophosphate samples with composition 43.8Na₂O12.5Al₂O₃43.8P₂O₅ were prepared by the sol–gel route using different precursors and working in different pH ranges from pH < 1 up to pH > 10. The structures of the gels and of the corresponding glasses were investigated by solid state NMR and compared to that of a glass with the same composition prepared by a traditional melting process. In addition to bulk materials, thin films were deposited by dip coating on silica glasses. Applying secondary neutral mass spectrometry (SNMS), the expected elements and residual carbon were identified. The surfaces of the coatings and fracture surfaces of bulk material were investigated using atomic force microscopy (AFM). Solid state NMR revealed that samples prepared via a lactate route exhibited local Al and P environments closest to that of the melt-prepared glass, with the highest extent of Al-O-P connectivity.     

Crystal structure,infrared and raman spectra of tripotassium trisaccha-rinate dihydrate,K<Subscript>3</Subscript>(C<Subscript>7</Subscript>H<Subscript>4</Subscript>NO<Subscript>3</Subscript>S)<Subscript>3</Subscript>·2H<Subscript>2</Subscript>O

The crystal structure of tripotassium trisaccharinate dihydrate, K₃(C₇H₄NO₃S)₃·2H₂O, is triclic, space group\(P \bar 1, Z = 2\). It consists of three crystallographically independent potassium and saccharinato ions as well as two structurally different water molecules. Potassium coordination polyhedra are irregular, with K1 and K3 six-coordinated and the third one K2 seven-coordinated. The K?O distances range from 2.652(9) to 3.100(2) Å(mean: 2.790 Å) whereas the K?N distance is 3.025(3) Å. The water molecules W2 is disordered over three positions with occupancies of approximately 0.6, 0.2 and 0.2. The hydrogen atom (H1W1) of the ordered water molecule (O1W) is hydrogen bonded to the sulfonyl oxygen atom (O11) (R(O...O)=2.976(3) Å), whereas the other hydrogen atom (H2W1) is bifurcated to the carbonyl oxygen atom (O13) (R(O...O)=2.851(3) Å) and the disordered water molecules (O23W) (R(O...O)=3.067(12) Å). The carbonyl oxygens (O13, O23 and O33) and one of the disordered water molecules (O22W) are involved in C?H...O hydrogen bonds (R(C?H...O)=3.027(4)–3.304(9) Å). Structural characteristics of the studied compound are compared with the analogous trisodium trisaccharinate dihydrate and dipotassium sodium trisaccharinate monohydrate. Infrared and Raman spectra of the title compound have been analyzed in relation to the structure, and compared with the spectra of trisodium trisaccharinate dihydrate.     

Concentration Space of Homogeneous Garnet in the System Ga<Subscript>2</Subscript>O<Subscript>3</Subscript>–(Y,Bi)<Subscript>3</Subscript>(Fe,Ga)<Subscript>5</Subscript>O<Subscript>12</Subscript>–Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>

The concentration space of homogeneous garnet in the system Ga₂O₃–(Y, Bi)₃(Fe, Ga)₅O₁₂–Fe₂O₃ was determined by X-ray powder diffraction analysis. The obtained results expand the knowledge of the possible variations of cation ratios Y : Bi : Fe : Ga in garnet, which can be used for searching for and creating new stable magneto-optical materials.     

Phase formation in Li<Subscript>2</Subscript>MoO<Subscript>4</Subscript>-K<Subscript>2</Subscript>MoO<Subscript>4</Subscript>-MMoO<Subscript>4</Subscript> (M = Ca,Pb, Ba) systems and the crystal structure of α-KLiMoO<Subscript>4</Subscript>

Solid-phase interactions in Li₂MoO₄-K₂MoO₄-MMoO₄ (M = Ca, Pb, Ba) systems were studied, and the subsolidus regions of these systems were triangulated. The lead and barium systems were studied in a more detailed way to discover that, along KLiMoO₄-K₂M(MoO₄)₂ (M = Pb, Ba), KLiMoO₄-PbMoO₄, and Li₂MoO₄-K₂Ba(MoO₄)₂ quasi-binary sections, there are homogeneity regions reaching 6–11 mol % based on K₂M(MoO₄)₂ and lead molybdate. Triple molybdates are formed in none of the systems, which is verified by experiments on spontaneous crystallization from solution in melt. Crystallization experiments yielded crystals of potassium dimolybdate and simple and double molybdates from the boundary systems. The crystal structure was solved for a hexagonal KLiMoO₄ phase: (Na,K){ZnPO4}, a = 18.8838(7) Å, c = 8.9911(6)Å, Z = 24, space group P6₃, R = 0.065. The structure comprises a three-dimensional tridymite framework built by an alternation of corner-sharing LiO₄- and MoO₄ tetrahedra wherein voids are occupied by potassium cations.     

A theoretical investigation on the structures and stabilities of C<Subscript>60</Subscript>X<Subscript>18</Subscript> and C<Subscript>70</Subscript>X<Subscript>10</Subscript> (X = H,F, Cl,and Br)

A density functional theory study was performed on fullerene derivatives C₆₀X₁₈ and C₇₀X₁₀ (X = H, F, Cl, and Br). The calculated results show that the lowest energy isomers are IPR-satisfying for C₆₀X₁₈ (X = H, F, Cl, and Br). It is found that the addition patterns of X (X = Cl and Br) are different from those of X (X = H and F) for C₆₀, demonstrating that the stability of fullerene derivatives is partly attributed to the steric repulsion and electronegativity of added atoms. However, the lowest energy isomers are IPR-violating for C₇₀X₁₀ (X = H, F, and Cl), suggesting that many more fullerene derivatives may violate the isolated pentagon rule.     

Synthesis and transport properties of perovskite-like phases (Sr,Ba)<Subscript>4</Subscript>E<Subscript>2</Subscript>Nb<Subscript>2</Subscript>O<Subscript>11 ± δ</Subscript> (E = Mn,Cr, Cu)

Synthesis of (Sr, Ba)₄Э₂Nb₂O_{11 ± δ} where E = Mn, Cr, Cu and solid solution (Sr_1?y Cu_y)_{6 ? 2x} Nb_{2 + 2x} O_{11 + 3x} is performed. By measuring the overall conductance of some solid-solution compositions it is established that the conductance increases with the cubic-lattice parameter and concentration of oxygen vacancies. Values of the conductance in humid air at T < 700°C are shown to increase as compared with dry air. Mass spectrometry analysis confirms the possibility of water incorporation into the complex-oxide structure out of a gas phase. Complex certification of samples of the composition (Sr, Ba)₄E₂Nb₂O₁₁ where E = Mn, Cr, Cu is performed. It is established that the decrease in the overall electroconductance occurs in the series Sr₄Mn₂Nb₂O₁₁ > Ba₄Mn₂Nb₂O₁₁ > Sr₄CrMnNb₂O₁₁ > Sr₄Cu₂Nb₂O₁₁. Investigation of the overall electroconductance in dry and moist atmospheres shows that the effect of humidity exerts no influence on the values of the overall electroconductance. The oxygen-ion constituent of conductance is determined by the Arzhannikov method and is also evaluated from a σ,pO₂ dependence. It is established that the presence of an element with a variable oxidation degree for compositions of the type Sr₄E₂Nb₂O₁₁ leads to an increase in the contribution made by the electronic constituent. In so doing, the magnitude of the oxygen-ion conductance practically does not alter. Thermal and mass spectrometry analyses show that, for the Sr₄E₂Nb₂O₁₁ compositions where E = Mn, Cr, Cu, there occurs no water intercalation into structure, correspondingly, there is observed no appearance of a protonic constituent of conduction.     

Structure of bismuth oxoborate Bi<Subscript>4</Subscript>B<Subscript>2</Subscript>O<Subscript>9</Subscript> at 20, 200, and 450°C

Single crystals of bismuth oxoborate Bi₄B₂O₉ have been grown by slowly cooling the melt of a stoichiometric Bi₂O₃ + H₃BO₃ mixture. The structure of the borate (monoclinic space group P2₁/c, a = 11.107 Å, b = 6.629 Å, c = 11.044 Å, β = 91.04°, Z = 4) has been studied at 20, 200, and 450°C. The structure is described not only in terms of full BiO₆ ^? and BiO₇ polyhedra but also in terms of truncated BiO₃ ^? and BiO₄ ^? polyhedra and BO₃ triangles, as well as oxo-centered OBi₃ triangles and OBi₄ tetrahedra. It is shown that both the B-O and Bi-O bond lengths are practically unaffected by temperature. Only the angles between polyhedra change with temperature, being responsible for the strong anisotropy of Bi₄B₂O₆ thermal expansion, which was measured by high-temperature powder X-ray diffraction: α₁₁ = 20, α₂₂ = 15, α₃₃ = 6 × 10^?6 °C^?1, and μ = (c, α₃₃) = ?19°.     

Phase equilibria,water dissolution,and peculiarities of charge transfer in Ca-doped La<Subscript>2</Subscript>Zr<Subscript>2</Subscript>O<Subscript>7–α</Subscript>

A series of oxides La_{2 - x} Ca _x Zr₂O_7–α (x = 0.00, 0.05, 0.10, 0.15, 0.20) is synthesized. It is found that in samples with the calcium content x = 0.15, 0.20, the second phase Ca_0.9La_0.2Zr_0.9O₃ is present in the fraction increasing with the increase in x. The solubility limit of calcium to form solid solutions based on La₂Zr₂O₇ corresponds to x = 0.1. By high-temperature gravimetry, the proton concentration in La_1.95Са_0.05Zr₂O_7–α is obtained as a function of temperature in the interval of 300–950°С in Н₂О–О₂ atmosphere. According to temperature programmed desorption studies, in the temperature range of 400–900°С at least two types of OH defects with different binding energies are present in the oxide lattice. The temperature dependences of conductivity are obtained for La_1.95Са_0.05Zr₂O_7–α in dry and humid air atmosphere in the temperature range of 350–800°С by the method of impedance spectroscopy. The electrolyte conductivity in humid air is shown to substantially exceed the corresponding values in dry air, which can be associated with manifestation of protonic conductivity in humid atmosphere. The dependences of oxide conductivity on the oxygen content in the gas phase are determined. The conductivity is divided into its ionic and hole components.     

Four-component reciprocal system Na,K∥F,CO<Subscript>3</Subscript>, WO<Subscript>4</Subscript>

The four-component reciprocal system Na,K∥F, CO₃, WO₄ has been studied using differential thermal analysis in combination with projective and differential geometry. The a priori prediction of the crystallization path (CP) shows six quaternary invariant points; of them, three are eutectics and the others are peritectics. The dominant exchange and complexing reactions have been recognized. The following four-component systems have been studied: (NaF)₂-(KF)₂-K₂CO₃-K₃FWO₄ (1), (NaF)₂-K₂CO₃-K₂WO₄-K₃FWO₄ (2), (NaF)₂-Na₂CO₃-Na₂WO₄-K₂WO₄ (3),, and (NaF)₂-Na₂CO₃-K₂CO₃-K₂WO₄ (4); the coordinates of all quaternary invariant points have been determined.     

<Superscript>35</Superscript>Cl NQR for the SbCl<Subscript>3</Subscript> complex with aniline,SbCl<Subscript>3</Subscript>·NH<Subscript>2</Subscript>C<Subscript>6</Subscript>H<Subscript>5</Subscript>

The temperature dependence of the ³⁵Cl NQR frequencies and spin-lattice relaxation times has been investigated for a trigonal-bipyramidal vn complex SbCl₃·NH₂C₆H₅. Thermally activated motion of chlorine atoms (pseudorotation) was not revealed in the complex, in contrast to the vπ complexes of SbCl₃ with related molecular structures. The high potential barrier of pseudorotation in the aniline complex is likely to be due to the unusually high nonequivalence of Sb-Cl chemical bonds.     

Exohedral Silicon Fullerenes: Si<Subscript>60</Subscript>Pn<Subscript>60</Subscript> and Si<Subscript>80</Subscript>Pn<Subscript>60</Subscript> (Pn = P,As, Sb and Bi)

Based on density functional theory (DFT) calculations, we predict that the icosahedral structures of the silicon fullerenes Si₆₀ and Si₈₀ can be stabilized by 12 exohedral pentagons of group V-A unit Pn₅ (Pn = P, As, Sb or Bi). The 12 pentagons can fully passivate the dangling bonds associated with 12 pentagonal Si₅ rings on the silicon fullerene cages, thereby resulting in stable exohedral silicon fullerenes Si₆₀Pn₆₀ and Si₈₀Pn₆₀. Properties of the eight Si₆₀Pn₆₀ and Si₈₀Pn₆₀ clusters, including harmonic vibrational frequencies, electron affinity (EA), the HOMO–LUMO gap and NICS values, are computed. We find that all eight Si₆₀Pn₆₀ and Si₈₀Pn₆₀ fullerenes possess relatively large HOMO–LUMO gaps, high electron affinities, and that the Si₆₀Pn₆₀ fullerenes exhibit weak aromaticity. Among eight clusters examined, the exohedral fullerene I _h-Si₆₀P₆₀ possesses the largest cohesive energy per atom. Ab initio molecular dynamics (AIMD) simulation is performed to demonstrate thermal stability of the hollow cage structure of Si₆₀P₆₀ at the room temperature.     

Cutting Element LiF–LiVO<Subscript>3</Subscript>–LiKMoO<Subscript>4</Subscript>–KBr of the Quinary Reciprocal System Li,K||F,Br, VO<Subscript>3</Subscript>, MoO<Subscript>4</Subscript>

The cutting element LiF–LiVO₃–LiKMoO₄–KBr of the quinary reciprocal system Li, K||F, Br, VO₃, MoO₄ was studied by differential thermal analysis. The composition and melting point of the alloy corresponding to a quaternary eutectic were determined (7.0 mol % LiF, 32.0 mol % LiVO3, 47.7 mol % Li2MoO4 + K2MoO4, 12.3 mol % KBr, 410°С).