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卷 69, 编号 9 (2024)

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СИНТЕЗ И СВОЙСТВА НЕОРГАНИЧЕСКИХ СОЕДИНЕНИЙ

Chemosensor properties of Ti0.2V1.8CTx–V2O5–SnO2 nanocomposite

Simonenko Е., Mokrushin A., Nagornov I., Gorban Y., Simonenko Т., Simonenko N., Kuznetsov N.

摘要

The method of modification of accordion-like complex composition Ti0.2V1.8CTx MXene with tin(IV) and vanadium oxides by hydrothermal synthesis of SnO2 in water-alcoholic medium in the presence of dispersed particles of two-dimensional vanadium-titanium carbide was developed. The Ti0.2V1.8CTx-10mol.% SnO2 composition coating was carried out by microplotter printing on a specialized substrate followed by heat treatment in air at 300°С for 1h. For the formed layer Ti0.2V1.8CTx–V2O5–SnO2 nanocomposite chemosensor properties were comprehensively studied for a number of analyte gases: 100 ppm CO, NH3, NO2, benzene, acetone, ethanol, 1000 ppm H2, methane and 10% oxygen. Its high sensitivity and selectivity at operating temperatures of 150 and 200°С to nitrogen dioxide were shown: the responses to 100 ppm NO2 were 281 and 873%, respectively.

Žurnal neorganičeskoj himii. 2024;69(9):1213-1222
pages 1213-1222 views

Polyol synthesis of silver nanowires and their application for transparent electrodes fabrication

Simonenko N., Simonenko Т., Gorobtsov P., Arsenov P., Volkov I., Simonenko Е.

摘要

Polyol synthesis of thin silver nanowires has been studied and their suitability for the formation of transparent electrodes has been shown. The influence of stepwise heating of the reaction system on the position and shape of the absorption band associated with the surface plasmon resonance of the formed silver nanostructures has been determined. Using X-ray diffraction analysis it was found that the material does not contain crystalline impurities and has a face-centered cubic lattice. According to the scanning and transmission electron microscopy data, the main fraction is represented by elongated nanostructures with 10–15 μm length (however, there are also structures with length up to 20 μm) characteristic for silver nanowires of arc-shaped type. It is shown that the Ag nanowires obtained are quite thin (diameter is about 35–45 nm). Also in the composition of the material some amount of microrods of 1–3 µm length is observed, the diameter of which grows from 70 to 150 nm with decreasing length. In smaller quantities there is also an admixture of zero-dimensional particles, which are polyhedrons of various complexity. Atomic force microscopy has been used to study the surface of the film based on the obtained silver nanowires and the diameter of individual nanowire has been estimated. The optical properties and surface resistivity of the films based on the obtained silver nanowires were examined. It was found that the increase in transmittance at 550 nm from 73.9 to 90.3% is accompanied by an increase in the resistance value from 25 to 146 Ω/sq.

Žurnal neorganičeskoj himii. 2024;69(9):1223-1232
pages 1223-1232 views

Isotopic effect in the ir spectra of highly enriched amorphous silicon dioxide ASiO2 (A – 28, 29, 30)

Shumovskaya K., Komshina М., Sukhanov M., Plekhovich S., Plekhovich A., Otopkova P., Troshin O.

摘要

Amorphous silicon dioxide samples were obtained from silicon of natural isotopic composition, highly enriched silicon–28, –29, –30 with enrichment degrees from 99.29 ± 0.01 to 99.9980 ± 0.0010 at. %, and a mixture of silicon–28 and silicon–30. The samples were characterized by IR spectroscopy. The IR spectra of the samples show a shift of the known absorption bands of valence and strain vibrations for silicon–29 and Si–30 isotopes by 0.1–30.1 cm–1 to the low–frequency region concerning silicon–28. In silicon dioxide, a mixture of silicon–28, –30 isotopes, and natural isotopic composition, a deviation from the linear dependence of the frequency of vibration of monoisotopic patterns is observed. The positions of absorption band maxima in the model IR spectrum of silicon dioxide were calculated by the DFT method. The obtained results correlate with the experimental data with high accuracy. The values of the reduced mass and force constant of vibrating groups of atoms in silicon dioxide are determined, and the influence of these factors on the isotopic shift in the IR spectrum of silicon dioxide depending on the type of vibrations is established.

Žurnal neorganičeskoj himii. 2024;69(9):1233-1244
pages 1233-1244 views

Carboxonium derivatives of closo-decaborate anion [2,6-B10H8O2CC6H4R] based on aromatic carboxylic acids: synthesis and physicochemical properties

Kolbunova А., Klyukin I., Kubasov A., Selivanov N., Bykov A., Zhdanov A., Zhizhin K., Kuznetsov N.

摘要

The series of carboxonium derivatives of the closo-decaborate anion of the general form [2,6-B10H8O2CC6H4R], R=F, CH3, C3H7, C6H5 was obtained. To obtain the target systems, the interaction of the [B10H11] anion with aromatic carboxylic acids was used. This process took place in two stages through the formation of a monosubstituted derivative of the general form [2-B10H9OC(OH)C6H4R], R=F, CH3, C3H7, C6H5, followed by intramolecular cyclization, leading to the formation of the target disubstituted carboxonium derivatives. The structure of the [2,6-B10H8O2CC6H4-C6H5] anion was confirmed by X-ray diffraction analysis. The resulting carboxonium derivatives are capable of protonation to form neutral systems of the general form [2,6-B10H8O2CC6H4R(Hfac)]0, R=F, CH3, C3H7, C6H5. When a protonated carboxonium derivative of acetonitrile is added to a solution, a trisubstituted derivative of the general form [B10H7O2CC6H4R(NCCH3)]0 is formed.

Žurnal neorganičeskoj himii. 2024;69(9):1245-1253
pages 1245-1253 views

Luminescence features of multicomponent cubic fluoride pyrochlores doped with europium ions

Khaidukov N., Brekhovskikh М., Kirikova N., Kondratyuk V., Makhov V.

摘要

Ceramic samples of multi-component fluorides Na3CaMg3AlF14 and NaCaMg2F7 doped with europium ions have been obtained by solid-phase synthesis. A comparison of the XRD patterns for the obtained compounds confirmed that a new polymorphic modification with a cubic pyrochlore structure has been obtained for Na3CaMg3AlF14 fluoride, which differs from the polymorph of this compound with a rhombohedral structure described in the literature. The addition of NH4(HF2) before the last annealing provided reducing conditions for the stabilization of europium ions exclusively in the 2+ charge state. Eu2+ ions in the synthesized fluoride matrices emit luminescence with a band peak at about 395 nm due to 4f 65d–4f 7 interconfiguration transitions. In these matrices the Eu2+ ions form predominantly one type of optical centers, which provides a fairly narrow band-width of 4f 65d–4f 7 luminescence ~30 nm. Also, in the synthesized ceramics Eu2+ ions emit narrow-line luminescence with a dominant line at ~362 nm, associated with 4f7–4f7 intraconfiguration transitions from the lowest excited state 6P7/2 to the ground state 8S7/2. The synthesized ceramics demonstrate good temperature stability of Eu2+ 4f 65d–4f 7 luminescence with thermal quenching temperature T1/2 equal to 504 and 543 K for Na3CaMg3AlF14:Eu2+ (1.0 at. %) and NaCaMg2F7:Eu2+ (0.5 at. %), respectively. This property may be of interest for the practical application of these phosphors. Additional annealing of ceramics in an argon atmosphere with the addition of NaHF2 instead of NH4(HF2) led to a partial conversion of europium ions from a divalent to a trivalent state. As a result, a series of narrow luminescence lines appears in the red region of the spectrum due to intraconfiguration transitions 4f 6–4f 6 (5D07FJ) in Eu3+ ions.

Žurnal neorganičeskoj himii. 2024;69(9):1254-1266
pages 1254-1266 views

Bioglass 45S5 doped with Bi2O3 for medical use

Grishchenko D., Medkov М.

摘要

Bioglass 45S5 was doped with bismuth oxide in concentrations up to 40 wt.%. The amorphous nature of the synthesized glasses was confirmed by X-ray phase analysis. The influence of Bi2O3 on the properties of bioglass was studied. In a series of samples containing from 0 to 40 wt.% bismuth oxide, their characteristics change as follows: the pH values of the model medium during glass leaching decrease from 7.84 to 7.46; radiopacity increases from 1150 HU to values exceeding 11000 HU; chemical degradation drops from 1.299% to 0.424%; bioactivity decreases in the range of 0 – 10 wt.% and is absent in the range of 20–40 wt.% Bi2O3. Glasses containing up to 10 wt.% Bi2O3 can find application in reconstructive surgery. They have radiopaque and bioactive properties. Glasses containing 20–40 wt.% Bi2O3 have high radiopacity, chemical resistance, and a slight effect on the pH of the medium when dissolved. They may be promising as radiomodifiers in the treatment of malignant neoplasms using radiation therapy.

Žurnal neorganičeskoj himii. 2024;69(9):1267-1276
pages 1267-1276 views

Synthesis and study thermodynamic properties of germanates CaYb2Ge4O12 and CaLu2Ge4O12 the range 320–1000 K

Denisova L., Belokopytova D., Kargin Y., Vasil’ev G., Belousova N., Denisov V.

摘要

Solid-phase synthesis of CaYb2Ge4O12 and CaLu2Ge4O12 was carried out from the initial oxides of CaO, Yb2O3 (Lu2O3) and GeO2 by firing in air at temperatures of 1223–1423 K. The crystal structure of the synthesized germanates was determined by X-ray diffraction. The high-temperature heat capacity in the temperature range of 320-1050 K was measured by differential scanning calorimetry. It has been established that the obtained data on heat capacity are well described by the Mayr-Kelly equation:

Cp(CaYb2Ge4O12) = (416.4±0.40)+(72.67±2.30)×10-3T-(50.13±0.19)×105Т-2,

Cp(CaLu2Ge4O12) = (450.0±1.75)+(15.46±1.90)×10-3Т-(78.67±1.60)×105Т-2.

Based on these results, the main thermodynamic properties of oxide compounds were calculated.

Žurnal neorganičeskoj himii. 2024;69(9):1277-1283
pages 1277-1283 views

Synthesis of triethylammonium salts of amidine derivatives of closo-borate anions [B10H10]2– and [B12H12]2– and investigation of their cytotoxic properties

Ryabchikova M., Nelyubin A., Klyukin I., Karpechenko N., Zhdanov A., Zhizhin K., Kuznetsov N.

摘要

A series of amidine derivatives of closo-deca- and dodecaborate anions with triethylammonium cations were obtained in this work. The structure of the compounds was established by multinuclear NMR spectroscopy, ESI-mass spectrometry. Cytotoxicity was investigated for all obtained compounds by MTT method on 4 cell lines. It was shown that the nature of the cation does not affect the cytotoxicity of substituted closo-borates.

Žurnal neorganičeskoj himii. 2024;69(9):1284-1290
pages 1284-1290 views

Synthesis, crystal structure and thermodynamic properties of Ca3Y2Ge3O12 germanate

Denisova L., Belokopytova D., Kargin Y., Vasil’ev G., Denisov V., Beletskii V.

摘要

Orthogermanate Ca3Y2Ge3O12 has been prepared by solid-phase method from CaCO3, Y2O3 and GeO2 by firing in air at a temperature of 1773 K. Using X-ray diffraction, its crystal structure was clarified (sp. gr. Ia3¯d, a =12.80255(14) Å, V = 2098.34(7) Å3). The high-temperature heat capacity of oxide compound has been determined in the temperature range 320–1000 K by differential scanning calorimetry and the experimental data have been used to evaluate thermodynamic properties of Ca3Y2Ge3O12.

Žurnal neorganičeskoj himii. 2024;69(9):1291-1295
pages 1291-1295 views

КООРДИНАЦИОННЫЕ СОЕДИНЕНИЯ

Structural organization and thermal behavior of the compounds Rb3 (SbF3)(Zr2F11) · 0.5H2O and Rb3 (SbF3)(Zr2F11)

Gerasimenko А., Antokhina T., Savchenko N.

摘要

The compound Rb3(SbF3)(Zr2F11)·0.5H2O has been synthesized, its structure and the structure of its dehydration product have been studied. The Rb3(SbF3)(Zr2F11)·0.5H2O compound has a unique fluoridozirconate framework structure built from circular tetrameric fragments (Zr4F24) linked to each other at the vertices by bridging fluorine atoms. Inside the tetrameric fragments, the ZrF8-polyhedra are linked to each other along common edges. The zirconium framework 3[Zr2F11]3– is linked by fluoride bridges Zr–F–Sb from the second coordination sphere of antimony atoms. The structure of the dehydrated compound Rb3(SbF3)(Zr2F11) is a three-dimensional framework consisting of infinite chains of the 1[Zr2F11]3– composition of ZrF7-polyhedra bonded along the edges and vertices. The chains are linked to each other into a 3D framework by Zr–F–Sb bridges from the second coordination sphere of antimony atoms. In the temperature range 247–256 K, the compound Rb3(SbF3)(Zr2F11) undergoes a reversible phase transition from partially disordered high-temperature α-phase to ordered low-temperature β-phase. Taking into account fluorine atoms of the second coordination sphere and the lone electron pair coordination polyhedra are formed in structures around the antimony atoms in the form of distorted octahedra (SbEF5) and capped octahedra (SbEF6).

Žurnal neorganičeskoj himii. 2024;69(9):1296-1307
pages 1296-1307 views

Novel double complex salts [M(im) n][RuNOCl5] (M = Ni, Cu): synthesis, structure, thermal properties

Borodin А., Filatov E., Plusnin P., Kuratieva N., Korenev S., Kostin G.

摘要

Methods for the synthesis of new double complex salts [Cu(im)4][RuNOCl5], [Ni(im)6][RuNOCl5]·H2O and [Ni(im)4(DMF)2][RuNOCl5] have been developed and their crystalline crystalline properties have been determined. structure. The thermal properties of synthesized DCS were studied in inert and reducing atmospheres using synchronous TG–DTA/EGA–MS analysis and ex situ X-ray diffraction of intermediate and final thermolysis products. It has been established that thermal decomposition occurs in three stages. The final products of thermolysis of [Cu(im)4][RuNOCl5] in inert and reducing atmospheres are a mixture of copper and ruthenium, and the product of thermal decomposition of [Ni(im)6][RuNOCl5]·H2O in an inert atmosphere is a mixture of nickel and ruthenium. In the nickel-ruthenium system, upon thermolysis in a reducing atmosphere in the range of up to 400°C, it is possible to obtain a supersaturated solid solution of Ni0.27Ru0.73. Increasing the thermolysis temperature to 800°C leads to partial decomposition of the solid solution.

Žurnal neorganičeskoj himii. 2024;69(9):1308-1318
pages 1308-1318 views

ТЕОРЕТИЧЕСКАЯ НЕОРГАНИЧЕСКАЯ ХИМИЯ

Spin properties of chiral SiC nanotubes

Dyachkov P., Kulyamin P.

摘要

Using the relativistic linearized augmented cylindrical waves technique, the dependences of the band structure of single-walled SiC nanotubes on spin and chirality were calculated. It has been established that nanotubes are the wide-gap semiconductors with Eg equal to 2.26–3.15 eV, and the spin-orbit splittings of the valence and conduction band edges lie in the range of 0.05–3.5 meV. The energies of the spin-orbit gaps in righthanded and lefthanded enantiomers coincide, but their spin directions are opposite. Chiral nanotubes are determined that are most suitable for selective spin transport with potentially high fluxes of α- and β-electrons in opposite directions.

Žurnal neorganičeskoj himii. 2024;69(9):1319-1328
pages 1319-1328 views

ФИЗИЧЕСКИЕ МЕТОДЫ ИССЛЕДОВАНИЯ

Synthesis and thermodynamic properties of thulium titanate

Gagarin P., Guskov A., Guskov V., Khoroshilov A., Gavrichev K.

摘要

The temperature stages of the crystallization process of thulium titanate of pyrochlore structural type during heating of the hydroxide precursor obtained by the reverse precipitation method have been studied by DSC/TG, X-ray phase analysis and electron microscopy. The molar heat capacity of Tm2Ti2O7 was measured in the temperature range 2–1870 K and on the basis of smoothed heat capacity the calculation of thermodynamic functions at 0–1900 K and the Gibbs energy of formation from oxides and from elements were performed. The contribution to the heat capacity of the Schottky anomaly at 20–320 K is highlighted.

Žurnal neorganičeskoj himii. 2024;69(9):1329-1340
pages 1329-1340 views

НЕОРГАНИЧЕСКИЕ МАТЕРИАЛЫ И НАНОМАТЕРИАЛЫ

Preparation and chemosensor properties of nano–composite obtained by hydrothermal modification of Ti2CTx by hierarchically organised Co(CO3)0.5 (OH) ⋅ 0.11H2O

Simonenko Е., Mokrushin A., Nagornov I., Dmitrieva S., Simonenko Т., Simonenko N., Kuznetsov N.

摘要

The process of modification of Ti2CTx MXene multilayer by hydrothermal synthesis of bulk hierarchically organized formations of Co(CO3)0.5(OH)⋅0.11H2O has been studied. It is shown that under the chosen conditions MXene is partially oxidized with the formation of aggregates of titanium dioxide nanoparticles with a diameter of ~3–10 nm on its surface. The sensing properties of the obtained composite material at room temperature and relative humidity 65±3% to a wide range of gaseous analytes (50 ppm CO, benzene, acetone, ethanol, 2500 ppm H2, CH4, 5% O2 and 40 ppm NH3, NO2) were investigated. Increased sensitivity was found for the detection of 40 ppm NH3 and NO2: the responses were -91 and -63%, respectively. Some aspects of the detection mechanism are discussed. The results obtained show promising modification of multilayer MXene with semiconducting metal oxides and hierarchically formed bulk formations in order to improve its chemoresistive properties.

Žurnal neorganičeskoj himii. 2024;69(9):1341-1352
pages 1341-1352 views