Effect of the phase composition of the starting mixture on the formation of the layered perovskite-like compound Bi<Subscript>7</Subscript>Fe<Subscript>3</Subscript>Ti<Subscript>3</Subscript>O<Subscript>21</Subscript>

The effect of the phase composition of the starting mixture on the formation of the layered perovskite-like compound Bi₇Fe₃Ti₃O₂₁ in the Bi₂O₃-TiO₂-Fe₂O₃ system is reported. The rate-limiting process in the formation of this compound is reactant mass transfer to the reaction zone.     

Estimating the activation energy of the displacement of Mg atoms in the channels of B<Subscript>25</Subscript>C<Subscript>4</Subscript>Mg<Subscript>1.42</Subscript> crystals

The activation energy of displacement of Mg atoms through channels of B₂₅C₄Mg_1.42 crystals is estimated using quantum chemical calculations (DFT (B3LYP potential), RHF, and UHF methods, 3-21G basis set) of the element of the structure modeling the channel and location of Mg atoms in it. The changes in the activation energy at the replacement of Mg atoms by Na and Li atoms were estimated. The greatest decreasing in the activation energy was detected for Li atoms. The obtained results can be regarded as a theoretical background for development of conducting systems based on B₂₅C₄Mg_1.42 crystals.     

Mechanism of the nanocrystals formation of the spinel structure in the MgO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-H<Subscript>2</Subscript>O system under the hydrothermal conditions

Using the method of hydrothermal synthesis,the nanoparticles of magnesium-aluminum spinel were obtained with a crystallite size of 40–50 nm. The sequence was determined of the chemical transformations under hydrothermal conditions of the initial magnesium-aluminum hydroxides obtained by co-precipitation, leading to the formation of nanoparticles MgAl₂O₄.     

Theoretical study of the structure of the C<Subscript>60</Subscript>@C<Subscript>450</Subscript> nanoparticle and relative motion of the encapsulated C<Subscript>60</Subscript> molecule

The equilibrium state of the C₆₀@C₄₅₀ nanoparticle was studied. The compound was found to be stable during the encapsulation of C₆₀ tubelene. The motions of tubelene in the confinement potential field of a closed C₄₅₀ nanotube, namely, the translational motion along the tubule axis and the rotational motion were investigated in detail. It is predicted that there is a nanogyroscope inside C₄₅₀, rotating in the field of the C₆₀ capsule. Its quantized rotational states were calculated. The nanoparticle structure and energy were investigated by the tight binding method using modified parameters.     

Trends in the cation distribution in the structures of the compounds forming in the Ln<Subscript>2</Subscript>O<Subscript>3</Subscript>-GeO<Subscript>2</Subscript>-P<Subscript>2</Subscript>O<Subscript>5</Subscript> systems

The cationic networks in the structures of the initial oxides and all binary and ternary compounds forming in the Ln₂O₃-GeO₂-P₂O₅ systems have been studied. In the phase diagrams of the Nd₂O₃-GeO₂-P₂O₅ and Er2O₃-GeO₂-P₂O₅ systems, the regions of the structural influence of individual compounds with topologically identical cationic networks—anisotropic (A), combined (C), and isotropic (I)—are united into common areas. The A: C: I area ratio is 1: 1: 1 in the neodymium system and 1.7: 1: 3.4 in the erbium system.     

Influence of ZrO<Subscript>2</Subscript> on the physicochemical properties of the ZrO<Subscript>2</Subscript>-TiO<Subscript>2</Subscript> binary system

A series of ZrO₂-TiO₂ mixed oxides with different weight ratios (5, 20, and 30% ZrO₂) were prepared by wet impregnation of TiO₂-P25 Degussa with certain amounts of ZrO(NO₃)₂·6H₂O (Fluka) dissolved in deionised water. The samples were characterized by the XRD, , , , and BET methods. An increase in ZrO₂ content shifted the phase transition temperature (anatase into rutile) toward higher temperatures. X-ray diffraction using an Anton Paar XRK900 reactor chamber indicated that, in the case of samples containing ZrO₂, an additional diffraction peak appeared after cooling down to 25°C. This peak could be attributed to a polymorph of TiO₂ such as in the single crystal of anatase or hexagonal form of TiO₂ which appears in the presence of ZrO₂. Generally, the preparation of dioxide systems can modify the properties of pure compounds or generate new catalytic sites as a result of strong interaction between ZrO₂ and TiO₂ oxides. The binary systems exhibit advantages like strong acidity, extended specific surface area, and high thermal stability in comparison with TiO₂. The article is published in the original.     

Conformational structure of the tetrapeptide Boc–Aib–Leu–Leu–Aib–OMe–the central fragment of the nonapeptide antibiotic leucinostatin A

The conformational structure of the tetrapeptide Boc–Aib–Leu–Leu–Aib–OMe has been investigated by the PCILO method. The computational results show the formation of two closed β-turns, both of which are of type III, and the peptide backbone folds into a right-handed 3₁₀-helical conformation stabilized by two intramolecular 4 → 1 hydrogen bonds. The helix thus formed generates a pore of ～3 Å along helix axis with hydrophobic amino acid side chains located on the outside of the helix, and this tendency of leucine side chains may enable leucinostatin A to fit into the membrane bilayer. The pore thus formed is cation-selective, and through this pore, the cation can pass only in a single file.     

Effect of the production temperature on the structure of Si<Subscript>3</Subscript>N<Subscript>4</Subscript> nanofibers

The effect of the production temperature on the morphology and structure of Si₃N₄ nanofibers was investigated. It was shown that nanofibers produced in the temperature range of 1340–1360°C are amorphous while those produced at 1380°C and above are monocrystalline. Apart from the principal phase (α-Si₃N₄) the imide Si₂N₂NH was also found in the reaction products.     

Measurement of the rate constants of the reactions of the chlorine atom with C<Subscript>3</Subscript>F<Subscript>7</Subscript>I and CF<Subscript>3</Subscript>I using the resonance fluorescence of chlorine atoms

The rate constants of the reactions of the chlorine atom with C₃F₇I (k ₁) and CF₃I (k ₂) have been measured using the resonance fluorescence of chlorine atoms in a flow reactor at 295 K: k ₁ = (5.2 ± 0.3) × 10⁻¹² cm³ molecule⁻¹ s⁻¹ and k ₂ = (7.4 ± 0.6) × 10⁻¹³ cm³ molecule⁻¹ s⁻¹. No iodine atoms have been detected in the reaction products.     

EPR study of the nature of the impurity centers responsible for the scintillation properties of the Li<Subscript>2</Subscript>Zn<Subscript>2</Subscript>(MoO<Subscript>4</Subscript>)<Subscript>3</Subscript> crystal

The binary molybdate Li₂Zn₂(MoO₄)₃ of a new crystal type was characterized by EPR, optical spectroscopy, and X-ray diffraction methods. The crystals have the Pnma symmetry group and the lattice parameters a = 5.1139(5) Å, b = 10.4926(13) Å, c = 17.6445(22) Å; Z = 4. The crystals possess scintillation properties; emission is caused by the presence of impurity levels in the forbidden band. The EPR studies of the nature of the impurity centers responsible for the scintillation characteristics of the crystal showed that the centers were Cu²⁺ ions substituted for zinc ions in the oxygen octahedra. The directions of the main values of the g and tensors (g _zz , A _zz ) correspond to the direction of O-Cu-O of the oxygen octahedron distorted along the Z axis. The EPR spectra of the copper ions are described by the spin Hamiltonian with the parameters g _‖ = 2.38, g _⊥ = 2.06; A _‖ = 116 G, A _⊥ = 0 G.     

Effect of the alloying component MnO<Subscript>2</Subscript> on the type of V<Subscript>2</Subscript>O<Subscript>5</Subscript> electrocrystallization

The methods of polarization curves E-log I _a and atomic-force microscopy were used to study the mechanisms by which the alloying component MnO₂ affects the electrocrystallization of V₂O₅ in electrolysis from mixed solutions of salts of these metals.     

The dependence of the oxygen-exchange properties of Ce<Subscript>0.5</Subscript>Zr<Subscript>0.5</Subscript>O<Subscript>2</Subscript> on the method of synthesis

The oxygen-exchange properties of Ce_0.5Zr_0.5O₂ samples prepared by the traditional coprecipitation method with the use of a biotemplate (pine wood sawdust) were studied by the temperature-programmed reduction and oxidation methods. The use of the template and the presence of alkali and alkaline-earth metal cations in it provides a high mobility of oxygen and a high capacity with respect to oxygen in the biomorphic oxide. Impurities cause the segregation of Ce- and Zr-enriched phases under high-temperature treatment conditions, which worsens the redox properties of the biomorphic sample. Nevertheless, the ability of the biomorphic sample to play the role of an “oxygen buffer” remains high compared with the coprecipitated oxide subjected to similar treatments.     

Effect of the preparation method of the cathode material LiNi<Subscript>0.33</Subscript>Mn<Subscript>0.33</Subscript>Co<Subscript>0.33</Subscript>O<Subscript>2</Subscript> on the electrochemical characteristics of a lithium ion cell

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.     

Effect of the modifier ion on the properties of MgFe<Subscript>2</Subscript>O<Subscript>4</Subscript> and ZnFe<Subscript>2</Subscript>O<Subscript>4</Subscript> pigments

Magnesium and zinc ferrites have been prepared by the polymeric precursor method. The organic material decomposition was studied by thermogravimetry (TG) and differential thermal analysis (DTA). The variation of crystalline phases and particle morphology with calcination temperature were investigated using X-ray diffraction (XRD) and scanning electronic microscopy (SEM), respectively. The colors of the ferrites were evaluated using colorimetry. Magnesium ferrite crystallizes above 800°C, presenting a yellow- orange color with a reflectance peak at the 600–650 nm range, while zinc ferrite crystallizes at 600°C, with a reflectance peak between 650–700 nm, corresponding to the red-brick color.     

Dependence of the Physicochemical and Catalytic Properties of Ce<Subscript>0.5</Subscript>Zr<Subscript>0.5</Subscript>O<Subscript>2</Subscript> Oxide on the Means of Synthesis

The effect the means of synthesis have on the texture, phase composition, redox properties, and catalytic activity of binary oxide systems with the composition Ce_0.5Zr_0.5O₂ are studied. The obtained samples are characterized via BET, SEM, DTA, XRD, and Raman spectroscopy. A comparative analysis is performed of the physicochemical properties of biomorphic systems Ce_0.5Zr_0.5O₂ obtained using wood sawdust and cellulose as templates and the properties of binary oxides of the same composition obtained by template-free means. The catalytic properties of the obtained oxide systems Ce_0.5Zr_0.5O₂ are studied in the reaction of carbon black oxidation. It is shown that the texture of the oxide depends on the means of synthesis. When biotemplates are used, fragile porous systems form from thin binary oxide plates containing micro-, meso-, and macropores. Oxide obtained via coprecipitation consists of dense agglomerates with pores around 30 Å in size. In supercritical water, nanoparticles of metal oxide form that are loosely agglomerated. The intermediate spaces between them act as pores more than 100 Å in size. A system of single-phase pseudocubic modification is obtained using a cellulose template. The crystal lattices of all the obtained systems contain a great many defects. It is shown that the system prepared via synthesis in supercritical water has the best oxygen-exchange properties. A comparative analysis is performed of the effect the physicochemical properties of the samples have on their activity in the catalytic oxidation of carbon black.     

Changes in the local symmetry of the ReO<Stack><Subscript>4</Subscript><Superscript>−</Superscript></Stack> anion near the melting point of alkali metal perrhenates

Raman spectra of alkali metal perrhenates in the vicinity of the crystal-melt phase transition have been studied. A premelting region characterized by high-temperature activation of the reorientational mobility of perrhenate ions has been revealed.     

Chemical assembly of the heteronuclear pivalate complex with the Li<Superscript>I</Superscript> and Fe<Superscript>III</Superscript> ions

The heteronuclear complex [Fe₄Li₂(O)₂(Piv)10(H₂O)₂] (1, Piv is the pivalic acid anion) was obtained by refluxing Fe^III pivalates with Li^I pivalates in toluene and isolated as the 1?PhCH₃ solvate with a toluene molecule. According to X-ray diffraction data, complex 1 contains the {Fe₄Li₂O₂} core. The Mössbauer spectroscopy data indicate that the core comprises para magnetic Fe^III ions in the high-spin state located in the symmetric octahedral environment of oxygen atoms. Thermolysis of 1 studied by simultaneous thermal analysis demonstrated thermal stability of the complex up to 225 °С. The main end product of thermolysis at 600 °С is the mixed oxide LiFe₅O₈.     

The sequence of equilibrium phase states of the Tb-Mn-O system in the thermal dissociation of the TbMn<Subscript>2</Subscript>O<Subscript>5</Subscript> compound

Phase equilibria in the Tb-Mn-O system during the removal of oxygen from the TbMn₂O₅ compound in stages were studied by the static method on a vacuum circulation unit (973–1173 K) with subsequent X-ray analysis of quenched solid phases. The dissociation of TbMn₂O₅ was found to occur in three stages. The temperature dependences of equilibrium oxygen pressure were determined experimentally for the phase equilibria observed. The standard thermodynamic functions of the dissociation and formation from the elements of TbMn₂O₅ and TbMnO₃ were calculated.