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Vol 62, No 6 (2017)

Synthesis and Properties of Inorganic Compounds

Thin films of the composition 8% Y2O3–92% ZrO2 (8YSZ) as gas-sensing materials for oxygen detection

Simonenko N.P., Simonenko E.P., Mokrushin A.S., Popov V.S., Vasiliev A.A., Sevastyanov V.G., Kuznetsov N.T.

Abstract

The synthesis of hydrolytically active heteroligand precursors of the composition [M(O2C5H7)x(iOC5H11)y] (M = Zr4+ and Y3+) using zirconium and yttrium acetylacetonates was investigated. It was shown that the reactivity of the obtained precursors in hydrolysis and polycondensation depends on the composition of the coordination sphere. It was studied how thin films of their solutions are applied by dip coating to the surface of Al2O3 substrates with platinum interdigital electrodes and a microheater. A study was made of the effect of the crystallization conditions and thickness of the oxide coatings of the composition 8 mol % Y2O3–ZrO2 on their microstructure and sensor characteristics in oxygen detection.

Russian Journal of Inorganic Chemistry. 2017;62(6):695-701
pages 695-701 views

Effect of the synthesis conditions on the size of magnetite nanoparticles produced by high-temperature reductive hydrolysis

Dosovitskii A.E., Grishechkina E.V., Mikhlin A.L., Kirdyankin D.I., Novotortsev V.M.

Abstract

A study was made into the effect of the conditions (synthesis temperature, water content, iron salt(III) concentration, and nature of precipitant) of the synthesis of magnetite nanoparticles by high-temperature reductive hydrolysis of iron(III) salts in an ethylene glycol medium on their size and morphology. It was shown that is basically possible to carry out the direct synthesis of spherical particles with an average size of 55–170 nm while varying synthesis conditions. The obtained particles were characterized by X-ray powder diffraction analysis, and their magnetic properties were explored. The synthesized particles are ferrimagnets. The magnetic moments, numbers, and sizes of domains in magnetite particles of various sizes were found.

Russian Journal of Inorganic Chemistry. 2017;62(6):702-710
pages 702-710 views

Synthesis of Fe3O4@Au core–shell nanoparticles

Solovieva A.Y., Ioni Y.V., Baskakov A.O., Starchikov S.S., Avilov A.S., Lyubutin I.S., Gubin S.P.

Abstract

A new two-step synthesis of Fe3O4@Au core–shell nanoparticles stabilized in polyethylene glycol is described. The nanoparticles were characterized by transmission electron microscopy, X-ray powder diffraction, UV and Mössbauer spectroscopy. Fe3O4@Au nanoparticles featured both optical properties (they featured a plasmon resonance band) and magnetic properties (they responded to an external magnetic field), typical of individual gold and magnetite nanoparticles, respectively.

Russian Journal of Inorganic Chemistry. 2017;62(6):711-714
pages 711-714 views

SiO2 and TiO2 nanoparticles in Aerosol OT reverse microemulsions: Synthesis and characterization

Demidova M.G., Shaparenko N.O., Podlipskaya T.Y., Bulavchenko A.I.

Abstract

Stable SiO2 and TiO2 organosols were prepared by hydrolyzing tetraethyl orthosilicate (TEOS) in the presence of 6–12 M NH3 and titanium(IV) isopropylate (TTIP) in reverse microemulsions of 0.12–0.25 M bis(2-ethylhexyl) sulfosuccinate (Aerosol OT, AOT) in n-decane with the aqueous pseudophase content of 2–3 vol %, 0.018–0.090 M TEOS, and 0.15–0.55 vol %, 0.003–0.025 M TTIP. The degree of hydrolysis was monitored by IR spectroscopy (for TEOS) and spectrophotometry (for TTIP). Oxide nanoparticles were characterized by photon-correlation spectroscopy (PCS) (Dh = 8–100 nm) and laser electrophoresis (ζ-potential = 7.4–11.6 mV). The occurrence of surface potential made it possible to separate the oxides from the excess of surfactant by nonaqueous electrophoresis and to determine particle sizes (7–40 nm) by means of transmission electron microscopy (TEM).

Russian Journal of Inorganic Chemistry. 2017;62(6):715-722
pages 715-722 views

Ion transfer asymmetry in Nafion membranes with gradient distribution of acid salts of heteropoly acids

Osipov A.K., Volkov A.O., Safronova E.Y., Yaroslavtsev A.B.

Abstract

We describe the effect caused by the modification of Nafion membranes with nanoparticles of rubidium and cesium acid salts of phosphotungstic and silicotungstic heteropoly acids (HPAs) using layer-by-layer casting on the properties of the membranes depending on the dopant type and the percent modified layer thickness. The ionic conductivity and diffusion permeability of hybrid materials have been studied. The modification is shown to increase the ionic conductivity at low relative humidity. The highest conductivity is observed for the membranes where the modified layer amounts to 35–50% of the total membrane thickness. On the contrary, diffusion permeability is reduced upon modification. Asymmetric ion transfer is observed: the ion transfer rate from the modified layer is lower than from the unmodified layer. This asymmetry arises from the anion concentration gradient in the membrane, which is directed from the modified to unmodified side of the membrane. An asymmetric membrane oriented so that its modified side faces the anode can potentially increase the power of a fuel cell.

Russian Journal of Inorganic Chemistry. 2017;62(6):723-728
pages 723-728 views

Coordination Compounds

Atomic structure and bonding interaction in a layered molybdenum disulfide compound with trimethylphenylammonium cations

Goloveshkin A.S., Bushmarinov I.S., Korlyukov A.A., Lenenko N.D., Golub’ A.S., Eremenko I.L.

Abstract

The atomic structure of the layered nanocrystalline molybdenum disulfide compound with trimethylphenylammonium cations has been determined for the first time using X-ray powder diffraction analysis adapted for turbostratically disordered systems and quantum chemical density functional theory calculations. It has been demonstrated that, in this compound, a conducting modification of MoS2 monolayers is stabilized, which is metastable under common conditions. Bonding interaction inside the molybdenum disulfide layers as well as between these layers and organic cations, revealed in the framework of Bader’s atoms in molecules theory, has been considered.

Russian Journal of Inorganic Chemistry. 2017;62(6):729-735
pages 729-735 views

Onium salts of sulfur-containing oxyanions resulting from reaction of sulfur(IV) oxide with aqueous solutions of 1,2-diamines and morpholine

Khoma R.E., Gel’mbol’dt V.O., Ennan A.A., Baumer V.N., Puzan A.N., Koksharova T.V., Mazepa A.V.

Abstract

Reaction products have been isolated from SO2–L–H2O–О2 systems (L = ethylenediamine, N,N,N′,N′-tetramethylethylenediamine, piperazine, and morpholine) as onium salts [H3NCH2CH2NH3]SO4, [(CH3)2NHCH2CH2NH(CH3)2]SO4, [(CH3)2NHCH2CH2NH(CH3)2]S2O6 ⋅ H2O, [C4H8N2H4]SO3 ⋅ H2O, [C4H8N2H4]S2O6, [C4H8N2H4]SO4 ⋅ H2O, [O(C2H4)2NH2]2SO4 ⋅ H2O. The prepared compounds have been characterized by X-ray diffraction analysis, X-ray powder diffraction, IR and mass spectroscopy.

Russian Journal of Inorganic Chemistry. 2017;62(6):736-745
pages 736-745 views

Polymeric lithium(I) diaquabarbiturate: Crystal structure

Golovnev N.N., Molokeev M.S., Lesnikov M.K., Vereshchagin S.N.

Abstract

The lithium(I) catena-diaquabarbiturate complex [Li(H2O)2(HBA–O,O′)]n (I), where Н2ВА is barbituric acid, has been structurally characterized by X-ray diffraction (CIF file CCDC no. 1447689), and its thermal decomposition and IR spectrum have been studied. Crystals of complex I are monoclinic, a = 6.4306(7) Å, b = 16.720(1) Å, c = 7.1732(8) Å, β = 108.253(4)°, V = 732.5(1) Å3, space group P21/c, and Z = 4. One independent μ2-bridging HBA ligand is coordinated to two Li(I) ions via the two oxygen atoms of C4(6)=O carbonyl groups. Each Li+ ion is linked with two μ2-HBA ions and two terminal water molecules at tetrahedron vertices. μ2-HBA ions link tetrahedra into a chain. The structure is stabilized by multiple hydrogen bonds and π–π-interaction between HBA. The shift of ν(C=O) vibration bands in the IR spectrum of complex I in comparison with Н2ВА towards lower frequencies agrees with the coordination of HBA via oxygen atoms. The dehydration of complex I occurs in two stages in the regions of 100–150 and 150–240°C.

Russian Journal of Inorganic Chemistry. 2017;62(6):746-750
pages 746-750 views

Structural features of monomeric octahedral d2-rhenium(V) monooxo complexes with the oxygen atoms of bidentate chelate (О,S and О,С) acido ligands

Sergienko V.S.

Abstract

Some structural features of 12 mononuclear octahedral d2-Re(V) monooxo complexes (IХII) with the oxygen atoms of bidentate chelate (О,S) acido ligands (Lig) and a similar complex with the oxygen atom of a bidentate chelate (О,С) monoanionic ligand (XIII) have been considered. The O(Lig) atoms are in trans positions to О(oxo) ligands in eleven complexes IХ and XIII and in cis positions to oxo ligands in two complexes XI and XII. In all the cases, Re–Otrans bonds are longer than Re–Ocis (or Re–Ostand).

Russian Journal of Inorganic Chemistry. 2017;62(6):751-759
pages 751-759 views

Hexafluorosilicates of cobalt(II) complexes with dimethylsulfoxide and dimethylformamide

Cherkasova T.G., Bagryanskaya I.Y., Pervukhina N.V., Kurat’eva N.V., Medvedev V.V., Tatarinova E.S., Cherkasova E.V.

Abstract

New double complexes [Co(DMSO)6][SiF6] ⋅ 2H2O (I) and [Co(DMF)3(H2O)3][SiF6] ⋅ DMF (II) have been synthesized and studied by IR spectroscopy and X-ray diffraction. Crystals of complex I belong to the tetragonal symmetry system, space group R3̄, Z = 3, a = 11.8232(3) Å, c = 18.4699(5) Å, V = 2235.97(10) Å3, ρcalc = 1.573 g/cm3. Crystals of complex II are triclinic, space group P1̄, Z = 2, a = 8.6264(4) Å, b = 10.1419(4) Å, c = 13.9657(6) Å, α = 100.847(2)°, β = 98.549(2)°, γ = 93.479(2)°, V = 1181.71(9) Å3, ρcalc = 1.539 g/cm3.

Russian Journal of Inorganic Chemistry. 2017;62(6):760-765
pages 760-765 views

Bismuth complexes [p-Tol4P]2+[Bi2I8(THF)2]2–, [p-Tol4Sb]2+[Bi2I8(THF)2]2–, [p-Tol4P]2+[Bi2I8(DMSO)2]2–, [Bu4P]n+[(Bi2I7)n]n, [p-Tol4P]n+[(Bi2I7)n]n, and [p-Tol4Sb]n+[(Bi2I7)n]n: Synthesis and structure

Sharutin V.V., Sharutina O.K., Khisamov R.M., Senchurin V.S.

Abstract

The complexes [p-Tol4P]2+[Bi2I8(THF)2]2–, [p-Tol4Sb]2+[Bi2I8(THF)2]2–, [p-Tol4P]2+[Bi2I8(DMSO)2]2–, [Bu4P]n+[(Bi2I7)n]n, [p-Tol4P]n+[(Bi2I7)n]n, and [p-Tol4Sb]n+[(Bi2I7)n]n were synthesized by the reaction between bismuth iodides and tetrabutyl- and tetraphenylphosphonium, tetra-para-tolylphosphonium and -stibonium iodides in tetrahydrofuran, dimethyl sulfoxide, acetone, and ethyl cellosolve. The crystal structures of the synthesized complexes containing bi- and polynuclear anions with an octahedral coordination of bismuth atoms were characterized by X-ray diffraction.

Russian Journal of Inorganic Chemistry. 2017;62(6):766-776
pages 766-776 views

Self-assembling systems based on metallophthalocyanines and nitrogen-containing ligands

Filippova A.A., Voronina A.A., Vashurin A.S.

Abstract

Association of sulfonated derivatives of cobalt phthalocyaninate in solutions in the presence of nitrogen-containing organic ligands is studied. Ligand denticity and spatial structure are found to be the main factors controlling the association equilibrium between sulfonated metallophthalocyanines.

Russian Journal of Inorganic Chemistry. 2017;62(6):777-782
pages 777-782 views

Theoretical Inorganic Chemistry

Electronic properties of achiral and chiral gold nanotubes

Khoroshavin L.O., Krasnov D.O., D’yackov P.N., Kol’tsova E.M.

Abstract

The band structure of ten single-walled gold nanotubes of different radius and chirality angle have been calculated by the linearized augmented cylindrical wave method. For all tubes, the Fermi level crosses the half-filled band; therefore, the tubes are characterized by a metallic electronic structure. The band structure of the nanotubes changes relatively weakly with a change in nanotube structure. The valence band width for all the tubes is 9.1 eV. The density of states at the Fermi level remains unaltered with a change in chirality angle and decreases by 30% with an increase in radius from 3 to 12 Å.

Russian Journal of Inorganic Chemistry. 2017;62(6):783-789
pages 783-789 views

Tetramer structure of a lithium thiocyanate complex in triethylamine

Mikhailov G.P.

Abstract

The density functional theory B3LYP/6-31+G(d,p) method in the framework of the discrete-continuum model has been applied to study the tetramer structure of a lithium thiocyanate complex in triethylamine (Et3N) with the use of experimental and calculated manifestations of ion association in the vibrational spectrum of the anion. Analysis of topological characteristics of the electron density distribution at critical point (3,–1) of the [Li+NCS]4 and [Li+NCS]4Et3N complexes has been performed.

Russian Journal of Inorganic Chemistry. 2017;62(6):790-794
pages 790-794 views

Topology of the liquidus hypersurface of the phase diagrams of quaternary systems

Kosyakov V.I., Shestakov V.A.

Abstract

Consideration was made of structural features of the liquidus and solidus hypersurfaces of the isobaric melting diagrams of quaternary systems with a single liquid phase and solid phases of constant compositions which undergo neither phase transitions nor decomposition into other phases while cooling. An intimate relationship between the topologies of such hypersurfaces was noted. The oriented graph of the liquidus hypersurface can be obtained from the graph of the solidus hypersurface by drawing arrows on its edges in the direction of decreasing temperature along the corresponding monovariant lines or by labeling its vertices with symbols of types of invariant reactions. An example was given for constructing different variants of the melting diagram of a system that correspond to the same topology of the solidus hypersurface.

Russian Journal of Inorganic Chemistry. 2017;62(6):795-801
pages 795-801 views

Boron, carbon, and aluminum supertetrahedral graphane analogues

Steglenko D.V., Zaitsev S.A., Getmanskii I.V., Koval V.V., Minyaev R.M., Minkin V.I.

Abstract

The electronic and spatial structures of carbon, boron, and aluminum supertetrahedrane models of graphane have been studied by means of density functional theory methods in the supermolecular approximation (B3LYP/6-311G(df,2p)) and with imposing periodic boundary conditions (PBEPBE/6-311G (d,p), HSEH1PBE/6-311G (d,p)). Calculations predict that pure boron and aluminum structures are narrow-gap semiconductors. For supertetrahedral carbon graphane, calculations predict properties intermediate between the semiconductor and insulator properties. All bonds in the carbon system are two-center two-electron (2с–2е), while for the boron system, intratetrahedrane bonds are three-center two-electron (3с–2е), and intertetrahedrane bonds are common two-center two-electron bonds (2с–2е).

Russian Journal of Inorganic Chemistry. 2017;62(6):802-807
pages 802-807 views

Physical Methods of Investigation

Reaction of the [B10H9O2C4H8] anion with C-nucleophiles

Matveev E.Y., Akimov S.S., Kubasov A.S., Nichugovskii A.I., Nartov A.S., Retivov V.M., Zhizhin K.Y., Kuznetsov N.T.

Abstract

The reactions of 1,4-dioxane-substituted closo-decaborate anion ([B10H9O2C4H8]) with metal acetylenides, diethyl malonate, ethyl acetoacetate, triethyl orthoformate, acetylacetone, and malonodinitrile were studied. The reactions were shown to be accompanied with substituent ring opening and attachment of the corresponding pendant functional group. The obtained compounds were characterized by various physicochemical methods (IR and polynuclear NMR spectroscopy, ESI mass spectrometry).

Russian Journal of Inorganic Chemistry. 2017;62(6):808-813
pages 808-813 views

Synthesis and heat capacity study of stannates Dy2Sn2O7 and Ho2Sn2O7 in the range 370–1000 K

Denisova L.T., Irtyugo L.A., Kargin Y.F., Denisov V.M., Beletskii V.V.

Abstract

Stannates Dy2Sn2O7 and Ho2Sn2O7 are produced by solid-phase synthesis from Dy2O3 (Ho2O3)–SnO2 stoichiometric mixtures by calcining at 1473 K. The molar heat capacity of holmium and dysprosium stannates is measured by differential scanning calorimetry (DSC) in the temperature range 370–1000 K. The experimental data are used to calculate thermodynamic properties (enthalpy change H°(T)–H°(370 K), entropy change S°(T)–S°(370 K), and the reduced Gibbs free energy Φ°(T)) of the synthesized compound.

Russian Journal of Inorganic Chemistry. 2017;62(6):814-817
pages 814-817 views

Volatility and thermal stability of vanadyl β-diketonate complexes

Malkerova I.P., Makarevich A.M., Alikhanyan A.S., Kuz’mina N.P.

Abstract

Thermal behavior and thermodynamic characteristics of vanadyl β-diketonates—acetylacetonate VO(acac)2, dipivaloylmethanate VO(thd)2, and tris-hexafluoroacetylacetonate VO(hfa)2 (Hacac, 2,4-pentanedione; Hthd, 2,2,6,6-tetramethyl-3,5-heptanedione; Hhfa, 1,1,1,5,5,5-hexafluoro-2,4-pentanedione)—have been studied by thermal analysis and the Knudsen effusion mass spectrometry study of gas phase composition. The compounds have been shown to undergo congruent sublimation. Saturated vapor over the complexes has been shown to comprise monomeric VOL2 molecules. Absolute values of partial pressures and sublimation enthalpies of these compounds have been determined.

Russian Journal of Inorganic Chemistry. 2017;62(6):818-821
pages 818-821 views

EPR spectral study of copper(II) chelates with hetarylhydrazones of glyoxylic acid

Popov L.D., Tupolova Y.P., Borodkin S.A., Efimov N.N., Ugolkova E.A., Lukov V.V., Chetverikova V.A., Scherbakov I.N., Minin V.V.

Abstract

Structure of copper(II) chelates based on glyoxylic hetarylhydrazones containing benzazole (quinoxaline and phthalazine) fragments have been studied by EPR spectroscopy. Spectral parameters in polycrystalline state and dimethylformamide solutions have been determined. Spectral parameters of benzimidazole derivative are typical for square planar structure of the chelate node, while phthalazine derivative displays formation of polymeric structures due to reduction of copper(II) atom.

Russian Journal of Inorganic Chemistry. 2017;62(6):822-826
pages 822-826 views

Thermal stability of potassium fluorooxalatozirconates

Godneva M.M., Mikhailova N.M., Kuznetsov V.Y., Zalkind O.A.

Abstract

Thermal decomposition of fluorooxalatozirconates (FOxZs) K3ZrF5C2O4, K2ZrF4C2O4 ⋅ 2H2O, KZrF3C2O4 ⋅ 3H2O, and Zr4O3F2(C2O4)4 ⋅ 2H2O in air flow is studied. Crystalline K2ZrF4C2O4 and KZrF3C2O4 are detected. The decomposition onset temperature of anhydrous products goes down as the K/Zr molar ratio decreases. Disproportionation of potassium FOxZs both at the oxalate group yielding K2ZrF4C2O4 and ZrO2–x/2Fx, K2C2O4 and K3ZrF7 and at fluorine yielding K3ZrF7 and ZrO2 takes place. FOxZs can be used as precursors to produce fine-grained ZrO2 (baddeleyite).

Russian Journal of Inorganic Chemistry. 2017;62(6):827-835
pages 827-835 views

Facile deposition of Ag3PO4 nanoparticles on Bi2MoO6 nanoplates by microwave for highly efficient photocatalysis

Nualkaew P., Phuruangrat A., Kuntalue B., Dumrongrojthanath P., Thongtem T., Thongtem S.

Abstract

A simple microwave method has been successfully developed to effectively produce Ag3PO4/Bi2MoO6 nanocomposites. X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) have been employed to determine the phase and morphology of the as-produced products. The photocatalytic activities were tested through the rhodamine B (RhB) degradation under visiblelight radiation. The interaction between cubic Ag3PO4 nanoparticles and orthorhombic Bi2MoO6 nanoplates has been characterized by XRD and TEM. In this research, the as-produced heterostructure Ag3PO4/Bi2MoO6 nanocomposites display effective photogenerated charge transfer between Ag3PO4 and Bi2MoO6 which can improve charge separation. The 10.0 wt % Ag3PO4/Bi2MoO6 nanocomposites showed the highest photocatalytic performance as high as 4.36 times of the pure Bi2MoO6 sample.

Russian Journal of Inorganic Chemistry. 2017;62(6):836-842
pages 836-842 views

Physicochemical Analysis of Inorganic Systems

Na2SO4–NaCl–H2O system with a binary homogeneous critical point: Phase equilibria at 475–520°C and to 130 MPa

Urusova M.A., Valyashko V.M.

Abstract

Phase equilibria were studied at temperatures 475–520°C and a pressure to 130 MPa in the ternary system Na2SO4–NaCl–H2O with boundary binary subsystems of two types. In type 1 subsystems (the NaCl–H2O subsystem in this work), there are no critical phenomena in saturated solutions. Type 2 subsystems (the Na2SO4–H2O subsystem in this work) have terminal critical points p (G = L – \({S_{N{a_2}S{O_4}}}\)) and Q (L1 = L2\({S_{N{a_2}S{O_4}}}\)). It was shown that the ternary system contains two regions of three-phase equilibria ((G–L–S) and (L1–L2–S)), divided by a two-phase fluid region (F – \({S_{N{a_2}S{O_4}}}\)), and two types of monovariant critical curves ((G = L – \({S_{N{a_2}S{O_4}}}\)) and (L1 = L2\({S_{N{a_2}S{O_4}}}\))). With increasing temperature, these three-phase regions approach each other until the two-phase fluid equilibrium vanishes and the monovariant critical curves meet at a binary homogeneous critical point (G = L–S ⇔ L1 = L2\({S_{N{a_2}S{O_4}}}\)) at a maximal temperature of ~495°C and a pressure of ~75 MPa.

Russian Journal of Inorganic Chemistry. 2017;62(6):843-853
pages 843-853 views

Physical Chemistry of Solutions

Separation of palladium and europium upon extraction with phosphorylated calix[4]- and thiacalix[4]arenes from nitric acid and carbonate solutions

Torgov V.G., Us T.V., Lavrukhina S.A., Petrova N.I., Mazalov L.N., Kalinkin A.V.

Abstract

Separate and concurrent extraction of palladium and europium from nitric acid and carbonate solutions with calix[4]- and thiacalix[4]arenes, their phosphorylated derivatives, and mixtures have been carried out. Charge state of sulfur and oxygen donor atoms in the extractants have been studied by XPS, XES, and quantum chemical calculations. It has been experimentally confirmed that the electronic structure of substituents at PO group has no effect of on the charge state of sulfur atoms in phosphorylated thiacalixarenes and assumption on the possible electronic effect of bridging sulfur atoms on the charge state of phosphoryl oxygen in bifunctional extractants has been made. These results substantiate the method of combined extraction of Pd and Eu from nitric acid solutions and their separation with factor 2 × 103 upon carbonate back extraction of europium and are of interest for simplified (Purex) and promising (Carbex) processes.

Russian Journal of Inorganic Chemistry. 2017;62(6):854-861
pages 854-861 views