Phase formation and physicochemical properties of perovskite complex oxides based on bismuth ferrite

The effect of the cationic composition on the formation of perovskite solid solutions based on bismuth ferrite(Bi_{1 − x/3}□ _x/3)[Fe_{1 − x} Ti _x ]O₃ with x = 0.00–0.48, Δx = 0.03, has been studied. The homogeneity range of the perovskite phase under the conditions of the solid-phase synthesis of solid solutions has been determined, and the effect of the cationic composition on the physicochemical properties of solid solutions has been studied.     

Magnetic interactions in ternary cobalt oxides with cubic perovskite structure

Magnetic properties were measured on the cubic perovskite systems SrCoO_3?δ, (La_1?xSr_x)CoO₃ (0.5 ≦ x ≦ 1.0), and Sr(Co_1?xMn_x)O₃ (0 ≦ x ≦ 1.0). It is found that S²⁺ and La³⁺ ions strongly affect the spin state of the Co²⁺ ion and that the Mn⁴⁺ ion located at the octahedral site affects the spin state of Co⁴⁺ ion. The magnetic properties (T_c, T_θ, and σ) are explained by the magnetic interaction Co³⁺OCo³⁺, Co³⁺OCo⁴⁺, Co⁴⁺OCo⁴⁺, Mn⁴⁺OMn⁴⁺, and Mn⁴⁺OCo⁴⁺ in these systems.     

Simulation of non-equilibrium energy distributions of current carriers in proton-conducting oxides with perovskite structure

A simulation method based on the integral equation for the sticking probability of ion in well was discussed for its application to study energy distributions of protons carried in simple and complex perovskite-like structures. In the terms of the Wiener—Hopf computational technique, a numerical algorithm was developed to detect deviations of the energy distribution function from the Boltzmann distribution near the potential barrier peak due to random interaction of ion with the nearest environment. Being considered as non-equilibrium in this sense, the derived distributions essentially deviated from the equilibrium distribution for a wide energy loss range of protons carried from one lattice position to another. The developed simulation algorithm may be of methodological interest in general practice for numerical solution of the Wiener—Hopf equations, because the known solution techniques for integral equations of this type are inapplicable to the studied problems of electrochemical kinetics due to their essentially different boundary conditions.     

The vibrational spectra of complex oxides with a perovskite-type structure

Some aspects of the crystal chemistry and vibrational spectroscopy of complex oxides with a perovskite-type structure have been considered. The results of investigations of rhenium, tungsten, niobium, and tantalum complex oxides with a perovskite-type structure by vibrational spectroscopy methods (IR absorption, spontaneous Raman scattering) have been surveyed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2062–2070, December, 1994.     

Multivariate data analysis approach to understand magnetic properties of perovskite manganese oxides

Here we apply statistical multivariate data analysis techniques to obtain some insights into the complex structure-property relations in antiferromagnetic (AFM) and ferromagnetic (FM) manganese perovskite systems, AMnO₃. The 131 samples included in the present analyses are described by 21 crystal-structure or crystal-chemical (CS/CC) parameters. Principal component analysis (PCA), carried out separately for the AFM and FM compounds, is used to model and evaluate the various relationships among the magnetic properties and the various CS/CC parameters. Moreover, for the AFM compounds, PLS (partial least squares projections to latent structures) analysis is performed so as to predict the magnitude of the Néel temperature on the bases of the CS/CC parameters. Finally, so-called PLS-DA (PLS discriminant analysis) method is employed to find out the most influential/characteristic CS/CC parameters that differentiate the two classes of compounds from each other.     

钙钛矿型复合氧化物光催化研究进展

扼要叙述了钙钛矿型复合氧化物(ABO3)作为光催化剂的研究进展。包括结构,机理,制备,改性和研究现状。强调了结构与性能之间的关系并对其研究方向提出了自己的见解。     

Crystal structure and magnetic properties of dinuclear iron(III) complex with ONNO-donor ligand

A new dinuclear Fe(III) complex, [Fe(5-MeOL1)(OH)_0.86(CH₃O)_0.14]₂?2(CH₃OH), [H₂-5-MeOL1 = N,N′-bis(5-methoxy-2-hydroxybenzylidene)-2,2-dimethylpropane-1,3-diamine], 1 has been synthesized and characterized by single crystal structure analysis. The structure of 1 consists of two Fe(III) centers with one tetradentate schiff base ligand (N₂O₂) which are bridged by dihydroxo/dimethoxo groups to yield a Fe₂O₂ core. Complex 1 exhibits weak antiferromagnetic exchange interaction between Fe(III) ions with J = ?0.21 cm^–1.     

Synthesis,structure, and catalytic properties of Zr(IV) complex with trifluoroacetylacetone

Zirconium complex with trifluoroacetylacetone (Tfac) of the composition Zr(Tfac)₄(I) was synthesized and its structure was determined by X-ray diffraction. In the presence of polymethylaluminoxane, complex I is an active catalyst in ethylene polymerization to linear unbranched polyethylene. Crystals I are triclinic: a = 8.1600(16), b = 11.498(2), c = 15.766(3) Å, α = 99.20(3)°, β = 103.07(3)°, γ= 107.94(3)°, space group P \(\overline 1 \), Z = 2, ρ(calcd.) = 1.759 g/cm³, R = 0.0679. The structure consists of individual mononuclear Zr(Tfac)₄ complexes. The Zr atom coordinates eight O atoms of four β-diketonate ligands (Zr-O 2.17–2.20 Å). The complexes in a crystal are bonded by van der Waals interactions.     

Changes in electronic structure upon lithium insertion into the A-site deficient perovskite type oxides (Li,La)TiO3

Investigation on variation of the electronic structure accompanying the electrochemical lithium insertion into the perovskite type oxide, (Li,La)TiO3, has been carried out by X-ray absorption spectroscopy (XAS). During the electrochemical lithium insertion, titanium ion reduced its oxidation state from Ti4+ to Ti3+, while La3+ does not contribute to the reduction reaction resulting from Ti K-edge and La L3-edge XAS, respectively. Furthermore, O K-edge XAS showed marked spectral changes with electrochemical lithium insertion, indicating the electronic structure around oxide ion affected by lithium insertion reaction. From the XAS measurement, we have concluded the variation observed in O K-edge XAS was related to the strong interaction with inserted Li ion. To confirm this, first-principles band calculations were performed for the perovskite structure before and after electrochemical lithium insertion. The calculated results showed that the electron originated from inserted Li transferred to neighboring oxide ion locally as well as to Ti ion. This may be due to local neutralization effect of Li to reduce the electrostatic interaction in the crystal.     

Thermal properties of poly(tertiary phosphine oxides)

DTA and TGA (in air and in nitrogen) are presented for the poly(tertiary phosphine oxides), C₆H₅[(C₆H₅)P(O)CH₂CH₂]_nP(O)(C₆H₅)₂, where n = 1, 2, or 3.     

Crystal and electronic structure and magnetic properties of divalent europium perovskite oxides EuMO3 (M = Ti, Zr, and Hf): experimental and first-principles approaches

A comparative study of the crystal and electronic structure and magnetism of divalent europium perovskite oxides EuMO(3) (M = Ti, Zr, and Hf) has been performed on the basis of both experimental and theoretical approaches playing complementary roles. The compounds were synthesized via solid-state reactions. EuZrO(3) and EuHfO(3) have an orthorhombic structure with a space group Pbnm at room temperature contrary to EuTiO(3), which is cubic at room temperature. The optical band gaps of EuZrO(3) and EuHfO(3) are found to be about 2.4 and 2.7 eV, respectively, much larger than that of EuTiO(3) (0.8 eV). On the other hand, the present compounds exhibit similar magnetic properties characterized by paramagnetic-antiferromagnetic transitions at around 5 K, spin flop at moderate magnetic fields lower than 1 T, and the antiferromagnetic nearest-neighbor and ferromagnetic next-nearest-neighbor exchange interactions. First-principles calculations based on a hybrid Hartree-Fock density functional approach yield lattice constants, band gaps, and magnetic interactions in good agreement with those obtained experimentally. The band gap excitations are assigned to electronic transitions from the Eu 4f to Mnd states for EuMO(3) (M = Ti, Zr, and Hf and n = 3, 4, and 5, respectively).     

Synthesis,structure and magnetic properties of an iron(II) complex with nitronyl nitroxides

An iron(II) complex with nitronyl nitroxides, [Fe^II(dppNN)₂](BF₄)₂ · CH₃COCH₃ (1) (dppNN = 2,6-di(pyrazol-1-yl)-4-(4,4,5,5-tetramethyl-1-oxido-3-ylooxy-4,5-dihydro-3H-imidazol-2′-yl)pyridine) was synthesized. In 1 the central iron(II) ion was coordinated by two tridentate ligands with nitronyl nitroxides. Magnetic susceptibility measurements showed that χ_mT values below 130 K was almost temperature independent, while upon increasing temperature χ_mT values showed gradual increase, suggesting an occurrence of a spin transition from low to high spin state. Green light irradiation on powder sample at 5 K resulted in spin conversion (LIESST).     

Thermodynamic properties of complex oxides in the La-Ni-O system

Complex oxides La₂NiO_4+δ, La₃Ni₂O_7−δ, La₄Ni₃O_10−δ and LaNiO_3−δ, the members of Ruddlesden-Popper series La_n+1Ni_nO_3n+1, were prepared using citrate precursors. The stability range of LaNiO_3−δ in air as well as the oxygen nonstoichiometry of La₃Ni₂O_7−δ and La₄Ni₃O_10−δ as a function of temperature and oxygen partial pressure was determined by means of thermogravimetric technique. Decomposition temperatures of La₃Ni₂O_7−δ, La₄Ni₃O_10−δ and LaNiO_3−δ in air were determined by conductivity measurement method. The boundary of stability for La₄Ni₃O_10−δ was determined by EMF measurements of galvanic cell with oxygen conducting solid electrolyte. The isothermal (1400 K) projection of La-Ni-O system phase diagram to the plane “log(PO₂)-relative mole fraction of metal components” was suggested.     

Catalytic properties of spinel-type complex oxides in oxidation reactions

The catalytic activity of M^IM^II ₂O₃ spinel-type complex oxides (M^I = Cu, Ni, Mn, Zn, Mg, Co, M^II = Co, Cr, Al) in the oxidation of CO and ethylbenzene has been investigated. The Co-containing catalysts were more active than the Cr- and Al-containing catalysts. The nature of the cation influenced the catalytic activity. Higher activities were observed for the catalysts containing two transition elements. A correlation between the catalytic and adsorption properties was established.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1730–1732, October, 1994.     

Surface structure and properties of mixed fumed oxides

A variety of fumed oxides such as silica, alumina, titania, silica/alumina (SA), silica/titania (ST), and alumina/silica/titania (AST) were characterized. These oxides have different specific surface areas and different primary particle composition in the bulk and at the surface. These materials were studied by FTIR, NMR, Auger electron spectroscopy, one-pass temperature-programmed desorption with mass spectrometry control (OP TPDMS), microcalorimetry, and nitrogen adsorption. Nonlinear changes in the surface content of alumina in SA and AST and titania in ST and AST samples with increasing oxide content along with simultaneous changes in their specific surface area cause complex dependencies of the heat of immersion in water and desorption of water on heating on the structural parameters. Simultaneous analysis of changes in the surface phase composition, in the concentration of hydroxyls, and in the structural characteristics reveals that at a low content of the second phase the structural characteristics (e.g., S(BET)) are predominant; however, at a large content of these oxides the phase composition plays a more important role.     

Magnetic properties and crystal structure of the dichlorobis(1-allyltetrazole)cobalt(ii) complex

The cobalt(ii) chloro complex with 1-allyltetrazole (Alltz) Co(Alltz)₂Cl₂ was studied by the magnetic susceptibility measurements and X-ray diffraction analysis. The coordination polyhedron of the complex is a distorted octahedron formed by the N(4) atoms of two Alltz cycles and four bridging Cl atoms (coordination unit CoN₂Cl₄). Each chlorine atom is bound with two cobalt atoms giving rise to a crimped polymeric network. The Co(Alltz)₂Cl₂ complex is a weak ferromagnetic with T _N = 102±1 K and spontaneous magnetization _S(5 K) = 710±5 G cm³ mol^–1. Hysteresis effects, depending on the intensity of the magnetic field in which the sample was cooled, were detected.