Vol 61, No 9 (2016)

Low-agglomerated xerogels, ultrafine oxide powders with particle sizes of 12–20 nm, and uniform thin films with particle sizes of 8–14 nm are prepared in the CeO₂–Y₂O₃ system using liquid-phase low-temperature methods, namely via coprecipitation of hydroxides and cocrystallization of salts, sol—gel technology. A comparative characterization of the prepared xerogels and nanopowders is performed using a set of physicochemical analytical methods. A dependence of phase composition, microstructure, and particle size on synthetic parameters is elucidated.

A method is developed to incorporate europium into Mg–Al hydrotalcites, which are precursors for oxide catalysts of oxidative dehydrogenation (ODH) of alkanes; samples of oxide catalysts are prepared, where europium oxide and gallium, magnesium, aluminum, chromium, vanadium, molybdenum, and niobium oxides are contained in various combinations. The catalytic properties of these catalysts in the reactions of ethane, propane, and butane ODH are studied. The incorporation of europium into some of our studied multicomponent catalysts enhances the reaction selectivity and increases yields of desired products.

ZrO₂–SiO₂ xerogels have been synthesized through hydrolysis of a mixture of tetrabutoxyzirconium and tetraethoxysilane in a desiccator in a vapor of a 15% aqueous NH₃ atmosphere. ZrO₂–SiO₂–Cu(II) xerogels were synthethized analogously through joint hydrolysis of a mixture of the organometallic precursors and copper(II) chloride. The effect of synthesis conditions on the physical and chemical properties of the resulting material has been studied.

It was found that the recrystallization of the adduct Mn[(OOCC₅H₄)Mn(CO)₃]₂[O(H)Me]₄ from hot acetonitrile in the presence of benzene produces polymer [μ-(OOCC₅H₄)Mn(CO)₃]₄[μ-η²-(OOCC₅H₄)Mn(CO)₃]₂(NCMe)₂(OH₂)₂([μ-η²-(OOCC₅H₄)Mn(CO)₃]₂)[μ-(OOCC₅H₄)Mn(CO)₃]₄[μ-η²-(OOCC₅H₄)Mn(CO)₃]₂(OH₂)_2n. The obtained polymer was characterized by X-ray diffraction analysis.

The thermodynamic and geometric parameters of the molecular structures of macrotricyclic Tc(II), Ru(II), Rh(II), Pd(II), Ag(II), and Cd(II) complexes with the (NSSN)-coordination of the ligand donor sites formed by complexation of the corresponding M(II) ions with ethanedithioamide H₂N–C(=S)–C(=S)–NH₂ and ethanedial HC(=O)–CH(=O) have been calculated by the OPBE/TZVPQZP hybrid density functional theory method with the use of the Gaussian09 program package. The bond lengths and bond angles in these complexes have been reported, and it has been stated that the Rh(II) and Ag(II) complexes are nearly planar, the Tc(II), Pd(II), and Cd(II) complexes are slightly nonplanar, while the Ru(II) complex exhibits a rather considerable deviation from coplanarity. The additional five-membered chelate ring resulting from template cross-linking is either strictly planar (in the Tc(II), Rh(II), Pd(II), and Ag(II) complexes) or nearly planar (in the Ru(II) and Cd(II) complexes).

Nickel(II) dicarboxylates of unsaturated carboxylic acids (maleic (MalA), itaconic (ItA), acetylenedicarboxylic (ADCA), allylmalonic (AlMalA), glutaconic (GlutA), cis,cis-muconic (MucA) acids) were synthesized and characterized by thermal analysis and IR spectroscopy. The synthesized dicarboxylates were subjected to thermolysis, and the obtained nanocomposites were studied by transmission and scanning electron microscopy and X-ray diffraction. The synthesized metallopolymer nanocomposites were NiO and metallic Ni nanoparticles distributed over a stabilizing matrix. The formation enthalpy of dicarboxylates (ΔН_r^°) was calculated by the PM3 semi-empirical quantum-chemical method. The nanoparticle size was determined, and a relationship between the average nanoparticle diameter (d_avg) and ΔН_r^° was established. The microstructure and magnetic characteristics of the obtained nanocomposites, namely, the maximum and residual magnetization and the coercive force, were studied.

The crystal and local structures of compounds formed in the Dy₂O₃–HfO₂ system (at molar ratios from 1: 3 to 3: 1) in the course of isothermal annealing of X-ray amorphous mixed hydroxides at temperatures up to 1600°C have been studied. At the molar ratio Dy₂O₃: HfO₂ from 1: 3 to 1: 1, crystallization leads to formation of single-phase defect fluorite solid solutions nDy₂O₃ ∙ mHfO₂ with clearly pronounced nonequivalence of parameters of local environment of Dy³⁺ and Hf⁴⁺ cations. It has been found that Dy₂H₂O₇ (Dy₂O₃: HfO₂ = 1: 2) samples have a tendency to pyrochlore-type ordering in both the cationic and anionic sublattices.

Complex metal oxides with the composition LiNi_0.33Mn_0.33Co_0.33O₂ prepared by various methods: sol–gel method, solid-phase method, and thermal destruction of metal-containing compounds in oil were studied. The results of elemental analysis, TGA/DSC, powder X-ray diffraction, SEM, TEM, as well as the results of electrochemical testing of the cathodes based on the obtained materials are presented. The complex metal oxides LiNi_0.33Mn_0.33Co_0.33O₂ prepared by sol–gel processes and thermal destruction of metal-containing compounds in oil consist of primary nanosized crystallites with an average size of 90 nm covered by a nanometer carbon layer, which improves the electrochemical characteristics of lithium ion batteries.

The Li, Cs||F, NO₃ ternary reciprocal system was for the first time described and experimentally studied by differential thermal analysis and differential scanning calorimetry. Phase equilibrium states were determined, and so were the compositions and melting points of two ternary eutectics. Reactions describing the chemical interaction in the system were presented.

The phase diagrams of the ternary systems NaCl–NaBO₂–KCl, NaCl–KCl–Na₂CO₃, and KCl–NaBO₂–Na₂CO₃ and the quaternary system NaCl–NaBO₂–Na₂CO₃–KCl were studied by the calculation–experimental method and differential thermal analysis. Analytical models of phase equilibria were obtained, and the coordinates of ternary eutectics and a quaternary eutectic. It was shown that low-melting eutectic melts can be used as media for synthesizing oxide tungsten bronzes.

The Sn₂Sb₆S₁₁–PbSnSb₄S₈ system was studied by physicochemical analysis methods (differential thermal, X-ray powder diffraction, and microstructural analyses and microhardness and density measurements). It was found that this system is a quasi-binary section of the SnS–PbS–Sb₂S₃ ternary system of the eutectic type. The coordinates of the eutectic are 42 mol % PbSnSb₄S₈ and 600 K. In the studied system, regions of solid solutions were detected, which extend for solid solutions based on Sn₂Sb₆S₁₁ to 4 mol % PbSnSb₄S₈ (α) and for solid solutions based on PbSnSb₄S₈ to 6 mol % Sn₂Sb₆S₁₁ (β).

The composition and equilibria in solutions of the products of reaction of HfF₄(dmso)₂ with monodentate phosphoryl-containing bases L = Ph₃PO, Bu₃PO, and (Me₂N)₃PO in CH₂Cl₂ are studied by ¹⁹F NMR. Octahedral molecular complexes cis-[HfF₄L₂] and minor amounts of trans-[HfF₄L₂] and fac-[HfF₃L₃]⁺ cations were the main products for all ligands. The oxytrifluoride complex (μ-O)[HfF₃(Bu₃PO)₂]₂ and the [HfF₅(Bu₃PO)]^– anion were identified in the case of Bu₃PO. The conclusion about the formation of the hafnium oxytrifluoro complex was verified via hydrolysis of the product of reaction between HfF₄ and Ph₃PO upon exposure to air. As a result, (μ-O)[HfF₃(Ph₃PO)₂]₂ were detected; fine-structure ¹⁹F NMR resonance lines were obtained and the spin–spin coupling constant J_FF was measured for the first time. Hydrolysis via adding a Bu₄NOH solution in i-PrOH to the HfF₄L₂ solutions in CH₂Cl₂ did not yield the expected zirconium oxyfluoro complexes with the smaller number of fluorine atoms. Due to deeper hydrolysis, equilibrium in fluoride complexes shifted towards species with higher fluorine contents, [ZrF₅L]^– and [ZrF₆]^2–, resulting in the formation of Hf(O)_x(OH)_у(i-PrOH)_z complexes that were not observed in the ¹⁹F NMR spectra and the substitution of the released fluoride ions for molecular ligands in HfF₄L₂ complexes.