Ашық рұқсат
Рұқсат берілді
Тек жазылушылар үшін
Том 69, № 12 (2024)
СИНТЕЗ И СВОЙСТВА НЕОРГАНИЧЕСКИХ СОЕДИНЕНИЙ
CHEMICAL PRECIPITATION OF BaSn(OH)6 AND ITS THERMAL DESTRUCTION IN THE PROCESS OF BaSnO3 PREPARATION
Аннотация
The synthesis of barium hexahydroxostannate BaSn(OH)6 and its thermal destruction leading to the barium stannate BaSnO3 have been studied. It is shown that the most intensive decomposition of BaSn(OH)6 occurs in the temperature range of 200-650℃. Crystallization of BaSnO3 proceeds in a narrow temperature range (650-675℃), and the maximum of the corresponding exo-effect is located at 667℃. It was found that at 500℃ (within 60 min) BaSn(OH)6 completely decomposes with the formation of X-ray amorphous powder. When the material is kept at 600℃ (60 min), crystallization of barium stannate BaSnO3 with perovskite structure takes place. The crystalline impurity of barium carbonate contained in the semiproduct is preserved up to 600℃, and at temperatures from 700℃ the single-phase BaSnO3 is formed. The crystallization temperature of barium stannate can be reduced by 50-75℃ due to thermal exposure of the powder for 40-60 min. Holding the semiproduct at 600℃ for 60 min forms barium stannate with an average crystallite size of 21 ± 2 nm, and at 700℃ there is a slight increase in this parameter (up to 22 ± 2 nm).With increasing temperature up to 1000℃ there is intensification of crystallite enlargement process (up to 34 ± 3 nm). The obtained BaSnO3 powder, according to scanning electron microscopy data, consists of microrods (average length is about 85 μm; average diameter is about 10 μm). The surface of the rods is partially covered with spherical particles formed from smaller primary particles of about 30 nm in size.
Žurnal neorganičeskoj himii. 2024;69(12):1667-1676
1667-1676
PHOTOLYSIS AND PHOTODEGRADATION OF N-SUBSTITUTED PHTHALIMIDES WITH A CYMANTRENYL MOIETY
Аннотация
The photochemical behavior of substituted phthalimides with carboxylate groups associated with the cymantrenyl fragment was studied by infrared spectroscopy (IR), nuclear magnetic resonance (NMR) spectroscopy, UV-visible spectroscopy and cyclic voltammetry (CVA). During the formation of hemilabile dicarbonyl chelate complexes, a sharp change in the electronic, electrochemical and optical properties of compounds is observed. According to the dynamic light scattering (DLS) method, further irradiation of solutions of these complexes leads to the formation of previously undescribed stable nanoparticles in liquid media containing manganese in two degrees of oxidation Mn2+/Mn1+ and a phthalimide fragment associated with a Cp-ring coordinated or uncoordinated with manganese(I).
Žurnal neorganičeskoj himii. 2024;69(12):1677-1689
1677-1689
HYDROTHERMAL SYNTHESIS OF HIERARCHICALLY ORGANIZED MoS2 AND THE FORMATION OF FILMS BASED ON IT
Аннотация
The influence of hydrothermal synthesis parameters on the crystal structure and morphology of MoS2 particles has been shown. The results of synchronous thermal analysis showed that at the concentration of molybdenum cations of 0.05 mol/L, the increase in the duration of hydrothermal treatment leads to a decrease in the total mass loss (Δm), and the increase in c(Mo), on the contrary, results in a significant increase in the total Δm value. The dependence of the exo-effect maximum position, related to the MoS2 oxidation with the formation of MoO3, on the synthesis conditions was determined. According to X-ray diffraction analysis (XRD) data, the 1T-MoS2 phase is formed at minimum c(Mo) and duration of heat treatment. Increasing the time duration leads to the transformation of 1T-phase into 2H-MoS2. With increasing c(Mo), the 2H-phase transforms to 1T-MoS2 and further to 1T/2H-MoS2. The transformation of MoS2 structure was also analyzed by Raman spectroscopy. From the results of scanning electron microscopy (SEM), all samples represent flower-like nanostructures consisting of twisted nanosheets. According to transmission electron microscopy data, individual nanosheets with a length of 50-500 nm are formed after delamination of molybdenum disulfide structures. The microstructure of the obtained MoS2 film was studied by SEM and atomic force microscopy. Analysis of the film surface by Kelvin-probe force microscopy allows to establish the material has high electrical conductivity, and the work function value of the film surface was calculated.
Žurnal neorganičeskoj himii. 2024;69(12):1690-1704
1690-1704
LAYERED EUROPIUM AND YTTRIUM HYDROXYCHLORIDES: THERMAL DECOMPOSITION AND REHYDRATION
Аннотация
The dehydration-rehydration process of layered hydroxides is an example of a reversible chemical reaction involving rearrangement of the crystal structure. Products of thermal decomposition of layered rare earth hydroxides are known to interact under certain conditions with aqueous salt solutions and restore their original layered structure. In the present work, the effect of the temperature and duration of thermal treatment of the layered rare earth hydroxychlorides at 100–1150℃ on the interaction of the obtained products with aqueous sodium chloride solution was systematically studied for the first time. The main stages of the thermal decomposition of layered rare earth hydroxychlorideswere determined by the thermogravimetric analysis. Powder Xray diffraction analysis and energy-dispersive X-ray spectroscopy were used to determine the phase and the chemical composition of the products of thermal treatment and subsequent rehydratation of the layered hydroxides. It was shown that the presence of the rare earth oxychloride phase in the products of thermal decomposition was a critical factor for the recovery of the layered structure.
Žurnal neorganičeskoj himii. 2024;69(12):1705-1720
1705-1720
THE INFLUENCE OF HEAT TREATMENT CONDITIONS ON THE PRODUCTION OF ULTRAFINE IRON-ERBIUM GARNET POWDERS USING ANION RESIN EXCHANGE PRECIPITATION
Аннотация
Iron-erbium garnet is characterised by low magnetic losses, relatively high magnetisation, high thermal stability and it is used in radio electronics, computing, laser and microwave technology. This work proposes a method for the preparation of nanostructured Er3Fe5O12 powders, including the anion-exchange resin coprecipitation of erbium and iron(III) ions and further temperature treatment of the products. Optimal conditions for anion exchange resin precipitation of a stoichiometric highly active precursor were determined and the influence of the heat treatment regime on the formation process and stability of erbium ferrite-garnet nanoparticles was investigated. The resulting nanomaterials were characterised by X-ray phase analysis, electron microscopy, thermal analysis and Mossbauer spectroscopy. This synthesis method ensures the formation of iron-erbium garnet with a particle size of 26 ± 4 nm at a temperature of 800℃. The established patterns can be used to develop new methods for the synthesis of rare earth compounds with a garnet structure.
Žurnal neorganičeskoj himii. 2024;69(12):1721-1732
1721-1732
STRUCTURE AND THERMAL BEHAVIOR OF THE POTASSIUM OXOFLUORIDOZIRCONATE K2Zr3OF12
Аннотация
By heating an aqueous suspension of KZrF5, oxofluoridozirconate of the compositionK2Zr3OF12 was prepared and its structure and thermal decomposition were performed by DTA-TGA, XRD, IR and Raman spectroscopy. During the complete hydrolytic decomposition of K2Zr3OF12 at 620°C, a mixture of monoclinic phases K2ZrF6 and ZrO2 is predominantly formed. Experimental IR and Raman spectra of oxofluoridozirconate K2Zr3OF12 and its heating products were performed, systematized and analyzed. Based on the results of quantum-chemical calculations, bands in the experimental spectra were assigned.
Žurnal neorganičeskoj himii. 2024;69(12):1733-1742
1733-1742
CRYSTAL STRUCTURE OF INTERMETALLIC COMPOUNDS IN SYSTEMS Pd–(Cu, Ag, Au)–(In, Sn)
Аннотация
The crystal structure of ternary intermetallic compounds τ1 in the Pd-(Cu, Ag, Au)-Sn systems has been determined. It has been established that in the silver and gold systems they crystallize in a body-centered tetragonal cell with an ordering of atoms corresponding to the Al3Ti structural type, and in the copper system for the τ1 phase the VRh2Sn structure is formed, which is its additionally ordered derivative. The data available in the literature and obtained by the authors on the structures of binary and ternary compounds, which are ordered derivatives of a Cu-type structure, in Pd systems with group 11 elements and non-transition metals In and Sn are generalized and analyzed. It has been shown that they are formed at certain values of electron concentration (e/a): with the AuCu or Al3Zr structure types at e/a = 0.75, with the Al3Ti and VRh2Sn structure type at e/a from 0.8 to 1, and with the AuCu3 structure type at e/a = 1. The size factor affects the direction and extent of phase homogeneity regions.
Žurnal neorganičeskoj himii. 2024;69(12):1743-1751
1743-1751
SULFONIUM DERIVATIVES OF closo-DECABORATE ANION WITH CARBONYL GROUPS
Аннотация
The paper presents the synthesis of sulfonium derivatives of the closo-decaborate anion with exo-polyhedral carbonyl groups [B10H9S(CH2C(=O)R)2]- (R = Me, Ph, p-C6H4C1, Nh). The composition and structure are confirmed by elemental analysis, 11B, 1H, and 13C NMR spectroscopy. Crystal packings and intermolecular interactions for the compounds Bu4N[2-BwH9S(CH2COMe)2] and [Ag(FFh3)4][2-B10H9S(CH2COC6H4Cl)2] are studied using X-ray structural analysis and Hirschfeld surface analysis of the anions.
Žurnal neorganičeskoj himii. 2024;69(12):1752-1762
1752-1762
HYDROTHERMAL SYNTHESIS OF AQUEOUS SOLS OF NANOCRYSTALLINE HAFNIUM DIOXIDE STABILIZED BY LACTIC ACID AND THEIR ENZYME-LIKE ACTIVITIES
Аннотация
A method for obtaining aqueous sols of nanocrystalline hafnium dioxide (with hydrodynamic diameter 20-35 nm) stabilised by lactic acid (lactate ions) and characterised by high colloidal stability (zeta-potential -29 mV) has been developed. The method is based on the hydrothermal treatment of a previously obtained complex compound of hafnium with lactic acid in the presence of urea at temperatures of 180 and 220 degrees Celsius for 48 and 96 h. By chemiluminescence analysis in the model reaction of luminol oxidation it was found that nanocrystalline hafnium oxide in the composition of sols exhibits dose-dependent pro-oxidant activity towards hydrogen peroxide and thus exhibits peroxidase-like properties.
Žurnal neorganičeskoj himii. 2024;69(12):1763-1773
1763-1773
SYNTHESIS, STRUCTURE AND PROPERTIES OF Sr1-1.5x-yBix+yФ0.5xMo1-yVyO4 AND Sr1-1.5xBixФ0.5xMo1-yVyO4-d SOLID SOLUTIONS
Аннотация
The article is devoted to the study of synthesis conditions and structure details of cationand anion-deficient scheelite-releted solid solutions Sr1-1.5x-yBix+yФ0.5xMo1-yVyO4 and Sr1-1.5xBixФ0.5xMo1-yVyO4-d and their electrical conductive properties. For both series the homogeneity ranges were determined and the structural features were studied by X-ray powdwr diffraction and Raman spectroscopy. The morphology of ceramic samples was studied by scanning electron microscopy. The total electrical conductivity of the compounds was measured by impedance spectroscopy in the temperature range 400-650℃. To estimate the contribution of the electron and proton components to the total electrical conductivity of solid solutions, the electrical conductive characteristics were measured in a humid atmosphere and at various partial pressures of oxygen. The Arrhenius plots of the electrical conductivity are analyzed.
Žurnal neorganičeskoj himii. 2024;69(12):1774-1784
1774-1784
HYDROTHERMAL-MICROWAVE SYNTHESIS OF MnO/C COMPOSITE IN THE PRESENCE OF ASCORBIC ACID
Аннотация
For the first time composites based on manganese monoxide of cubic crystal system MnO/C were synthesized by hydrothermal-microwave treatment of aqueous solution of potassium permanganate with ascorbic acid and subsequent annealing of the precursor in an inert atmosphere at temperature of 500℃. It was found that the key parameter determining the features of composite formation is the molar ratio of the reaction mass components equal to Mn : C6H8O6 = 1 : (0.75-1.5). A mechanism of MnO/C composite formation is proposed. The maximum carbon content in the composite material is ≈ 3 wt. %. The main physicochemical characteristics of the synthesized composites were determined using the methods of X-ray phase and thermogravimetric analysis, Raman spectroscopy, scanning electron microscopy, low-temperature nitrogen adsorption. The study of the behavior of MnO/C as an anode material for a lithium-ion battery showed the efficiency of its use only at high current densities.
Žurnal neorganičeskoj himii. 2024;69(12):1785-1795
1785-1795
SYNTHESES, CRYSTAL STRUCTURES AND DIPOLE MOMENTS OF ZINC HALIDE COMPLEXES WITH METHYLUREA AND DIMETHYLACETAMIDE
Аннотация
Reactions of zinc halides with methylurea (MeUr) in aqueous solution result in formation of new coordination compounds [Zn(MeUr)2Cl2], [Zn(MeUr)2Br2], and [Zn(MeUr)2I2]. The coordination compounds were isolated and studied by X-ray diffraction and IR spectroscopy. In addition, we have studied the structure of the new polymorphic modification of the zinc bromide complex with dimethylacetamide (DMA) [Zn(DMA)2Br2]. The complexes are molecular, tetrahedral. Calculated dipole moments for the halide zinc complexes with methylurea and dimethylacetamide (with the PRIRODA quantum-chemical package) vary in the 9.3-9.7 D and 6.6-8.2 D ranges for zinc halide complexes with methylurea and dimethylacetamide, respectively.
Žurnal neorganičeskoj himii. 2024;69(12):1796-1804
1796-1804
CHANGES IN THE EXCITED STATE RELAXATION PATHWAY OF MONORUTHENIUM (II) BIPYRIDINE COMPLEXES WITH SUBSTITUTED IMIDAZO[4,5-f][1,10]PHENANTHROLINE LIGANDS UPON INTRODUCTION OF THE SECOND METAL CATION INTO COMPLEX COMPOSITION
Аннотация
A new type of heterobimetallic ruthenium-containing complexes based on thiophene-, pyridineand phenanthroline-containing ligand has been obtained and investigated. In the studied complexes, ruthenium(II) is bound to the 1,10-phenanthroline moiety and has a marked effect on the optical properties of the complex. The second metal cation is coordinated on the pyridine residue within the phenanthroline ligand. The coordination of the second cation results in a significant quenching of luminescence as a result of redistribution of electron density on the LUMO. It is also shown that the removal of the bridging thiophene fragment from the ligand composition significantly reduces the nucleophilicity of the pyridine nitrogen atom, and the latter loses the ability to coordinate doubly charged cations.
Žurnal neorganičeskoj himii. 2024;69(12):1805-1814
1805-1814
STRUCTURE AND RELATIVE STABILITY OF ISOMERS OF OXO- AND OXOHYDROXOALKOXO DERIVATIVES OF RHENIUM AND MOLYBDENUM RexMo4-xO6-n(ОН)n(OMe)10 (x = 0-4, n = 1, 2, 4)
Аннотация
Quantum chemistry methods were used to calculate heteronuclear clusters of oxoalkoxo-RexMo4-xO6(OMe)10 and oxohydroxoalkoxo-RexMo4-xO6-n(ОН)n(OMe)10, (n = 1, 2, 4) rhenium and molybdenum complexes. The core of the clusters is a rhombus of four metal atoms connected by bridging oxygen atoms along the sides and a small diagonal. Alkoxo groups occupy terminal positions. The structure and relative stability of the isomers of the positions of metal heteroatoms along the vertices of the rhombus are calculated. The theoretical differences in total energies relative to the most stable isomer, the length of metal-metal bonds, bond order indices and the sum of these indices for each isomer are determined. It has been established that in some cases, along with M-O-M' bridging bonds, metal-metal bonds are formed.
Žurnal neorganičeskoj himii. 2024;69(12):1815-1825
1815-1825
QUANTUM CHEMICAL MODELING OF INTERACTIONS OF Fe2O7 AND Fe2O9 CLUSTERS WITH H2 AND O2 MOLECULES
Аннотация
Quantum chemical calculations of the geometric and electronic structures of Fe2O7 and Fe2O9 clusters, as well as the reactions of interaction of Fe2O7 with H2 molecules, O2 and Fe2O9 with an H2 molecule in the gas phase were performed. Calculations were performed using the density functional theory method in the generalized gradient approximation using a triple-zeta basis. Differences in the thermal effects of these reactions during the interaction of clusters with H2 and O2 molecules were found. It was found that in the case of the reaction of Fe2O7 with an H2 molecule, the total spins of the initial reactants and the final products do not coincide, that is, spin relaxation occurs during the reaction.
Žurnal neorganičeskoj himii. 2024;69(12):1826-1833
1826-1833
DERIVATION OF A FORCE FIELD FOR COMPUTER SIMULATIONS OF MULTI-WALLED NANOTUBES. II. TUNGSTEN DISELENIDE
Аннотация
We propose a force field designed to model multi-walled WSe2 nanotubes whose size is beyond the capabilities of ab initio methods. The parameterization of interatomic potentials is successfully tested on single-walled and double-walled nanotubes, the structure of which is determined using non-empirical calculations. The above force field was applied to model the structure and stability of chiral and achiral multi-walled WSe2 nanotubes with diameters that approach experimental values. The properties of WSe2-based nanotubes are compared with the properties of analogous WS2-based nanotubes calculated using the force field, which was published in the previous paper I of this series. The interwall distances obtained from the simulations are in good agreement with recent measurements of these parameters for existing WS2 and WSe2 nanotubes. It is found that the inter-wall interaction contributes to the stabilization of multi-walled nanotubes slightly more in the case of WSe2 than in the case of WS2. Analysis of the deviation of the nanotube shape from the cylindrical one showed a close similarity of the structure of the tubes of both compositions.
Žurnal neorganičeskoj himii. 2024;69(12):1834-1847
1834-1847
PHYSICOCHEMICAL STUDY OF OXIDIZED MESOPOROUS CARBON MATERIALS
Аннотация
Physicochemical methods were used to study oxidized carbon materials that were obtained by treating mesoporous carbon material of the “Technosorb” brand with 2—30% solutions of hydrogen peroxide. Using IR spectroscopy, titrimetry and chemical analysis, it was shown that during the oxidation of carbon material, oxygen-containing groups (sp2-COOH, sp3-C-OH, sp2>C—OH, sp2>C=O, etc.) are formed on the surface of particles. The diffraction patterns of oxidized carbon materials show weak broad reflections typical of hydrated graphite oxide with a slight increase in the interplanar distance d002 . When the carbon material is oxidized, the specific surface area and free pore volume also increase without significant destruction of the nanoblocks of the carbon material structure.
Žurnal neorganičeskoj himii. 2024;69(12):1848-1863
1848-1863
EXPERIMENTAL STUDY OF STABLE HEXATOPE LiF-LiCl-LiBr-Li2CrO4-KCl-KBr OF THE QUINARY RECIPROCAL SYSTEM Li+,K+||F-,Cl-,Br-,CrO42-
Аннотация
This paper presents a theoretical and experimental study of the quinary reciprocal system Li+,K+||F-,Cl-,Br-,CrO42-. A phase tree was constructed. It has a branched structure and includes two stable pentatopes, stable hexatope and stable tetrahedral wich are separated by two stable secant tetrahedral and secant triangle. The LiF—LiCl—LiBr—Li2CrO4—KCl—KBr hexatope was experimentally studied by differential thermal analysis, X-ray phase analysis, and thermogravimetry. The nature of the physicochemical interaction was determined by studying the polythermal section passing through two low-melting quadruple eutectic points included in the faceting elements of the hexatope. It has been established, that solid solutions based on lithium and potassium chlorides and lithium and potassium bromides do not decompose. The characteristics of the minimum in the hexatope are defined. There are four crystallizing phases in the stable hexatope: LiF, Li2CrO4, LiClxBr1-x KClxBr1-x.
Žurnal neorganičeskoj himii. 2024;69(12):1864-1871
1864-1871
SYNTHESIS OF HIGH ELECTROCONDUCTIVE ZnO/CNT NANOCOMPOSITES WITH CHEMORESISTIVE RESPONSE AT ROOM TEMPERATURE
Аннотация
ZnO/CNT nanocomposites with CNT content from 0.01 to 10 wt.% were prepared using solvothermal synthesis. The thermal behavior of the obtained composites was studied at heating up to 850℃ using DSC/TGA. The phase composition was studied using XRD and Raman spectroscopy and the formation of hexagonal wurtzite phase was established. According to SEM data, zinc oxide nanoparticles are localized on the CNT surface. The temperature dependence of electrical resistance of ZnO/CNT nanocomposites was studied. It is shown that semiconductor or metallic type of conductivity is observed depending on the CNT content. The chemoresistive responses to a wide range of gases were studied at room temperature, the best sensitivity was shown by the sample with the lowest CNT content (0.01 wt. %).
Žurnal neorganičeskoj himii. 2024;69(12):1872-1881
1872-1881
SYNTHESIS OF Nb2AlC MAX-PHASE IN KBr PROTECTIVE MELT
Аннотация
The possibility of synthesis of Nb2AlC MAX-phase composition at varying temperature (900–1250℃) and molar ratio of initial reagents (powders of niobium, aluminum, carbon, as well as KBr salt, which performed a protective function in obtaining the target compound) was studied. By XRD it was found that at low synthesis temperatures (900–1100℃) only intermediate products are obtained, and at the synthesis temperature of 900℃ metallic niobium is also present. SEM and EDX-mapping data confirm the formation of MAX-phase at higher synthesis temperatures of 1200 and 1250℃. The effectiveness of decreasing the content of carbon in the initial mixture and increasing the aluminum content is shown. The thermal behavior in air current of the products obtained at temperatures of 900 and 1250℃ was studied.
Žurnal neorganičeskoj himii. 2024;69(12):1882-1891
1882-1891
CORRELATION BETWEEN ELECTRICAL PROPERTIES AND STRUCTURAL AND MORPHOLOGICAL CHARACTERISTICS OF SAMPLES IN THE QUASI-BINARY EUTECTIC SYSTEM Ba2In2O5-Ba2InNbO6
Аннотация
The structural and morphological properties of samples in the eutectic systemBa2In2O5—Ba2InNbO6 were studied when processed below and above the eutectic temperature. Has been determined the presence of a narrow region of homogeneity — solid solution Ba2In2-xNbxO5+x (x ≤ 0.05) and the formation of composites of composition (1 - y)Ba2In1.95Nb0.05O5.05 • yBa2InNbO6. In composites with y ≤ 0.15 for the main phase, a structure with a disordered arrangement of oxygen vacancies is stabilized. The total electrical conductivity in a dry air atmosphere is determined primarily by oxygen-ion transfer and increases for both solid solution and composites; the maximum increase by ~2 orders of magnitude is observed for composite samples with y = 0.15, 0.25, processed above the eutectic temperature. The increase in electrical conductivity is due to the combined influence of structural and morphological factors. Composites processed above the eutectic temperature are characterized by a special morphology — a layer of submicron-sized crystallites is formed on the surface of the grains of the main phase during crystallization of the eutectic, which determines the appearance of the compositional effect of electrical conductivity.
Žurnal neorganičeskoj himii. 2024;69(12):1892-1904
1892-1904