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New bifunctional cobalt catalysts for combined Fischer–Tropsch synthesis and hydroprocessing of hydrocarbons containing Pt were developed. To prepare catalysts in the form of a composite mixture, the FT synthesis catalyst Co-Al2O3/SiO2 and ZSM-5 zeolite in the H-form were used as metal and acid components, respectively, with boehmite as a binder. The catalysts were characterized by various methods, such as XRD using synchrotron radiation, SEM, EDS, TEM and TPR. The effect of the Pt introduction method on the particle size and conditions for cobalt reduction was studied. The testing of catalysts in Fischer–Tropsch synthesis was carried out at a pressure of 2.0 MPa, a temperature of 240 and 250 °C, an H2/CO ratio of 2 and a synthesis gas volumetric velocity of 1000 h−1. It is shown that the method of introducing a hydrogenating metal by adjusting the nano-sized spatial structure of the catalyst determined the activity in the synthesis and group and fractional composition of the resulting products. It is established that the presence of Pt intensified the processes of synthesis and hydrogenation, including isomeric products, and reduced the content of unsaturated hydrocarbons. The application of Pt by impregnation onto the surface of the metal component of the catalysts provided the highest productivity for C5+ hydrocarbons, and for the acidic component, it enabled maximum cracking and isomerizing abilities. [ABSTRACT FROM AUTHOR]

Based on the data of synchrotron and electron microscopic studies of deformed and annealed Russian zirconium alloys, the possibility of analyzing the structural-phase state and crystallographic texture of individual phases has been demonstrated. A qualitative and quantitative phase analysis of deformed and annealed tubes made of Zr-Nb-(Sn-Fe-O) alloys was carried out using diffraction patterns obtained with synchrotron radiation. The main α-Zr phase and the following additional phases: β-Nb, β-Zr, and the Laves phase (intermetallic compound Zr(Nb, Fe) 2 ), were found in the alloys. According to the results of texture analysis of all phases present in the alloy, the mechanisms of plastic deformation, recrystallization, and phase transformations of the main and additional phases were established. It is shown that during plastic deformation of the Zr-1%Nb alloy, a dynamic phase transformation β-Nb→α-Zr→β-Zr is observed. It is established that during recrystallization, larger grains of α-Zr are misoriented relative to the deformed matrix by rotating the prismatic axes around the basal axes by 30°, while fine grains are improved by polygonization and maintain the orientation of the deformed matrix. Processes for changing the orientation of grains of additional phases as a result of high-temperature annealing are also considered. [ABSTRACT FROM AUTHOR]

This article reports on a simple method for producing high-octane gasoline from CO and H2 on a Co-Al2O3/SiO2/HZSM-5/Al2O3 hybrid catalyst. In the selected pressure range (0.5, 1.0, and 2.0 MPa), it was found that a decrease in pressure and an increase in temperature contribute to an increase in the content of branched hydrocarbons. The optimal technological parameters of the process were determined to ensure high selectivity and productivity for C5–C10 hydrocarbons: pressure—1.0 MPa, ratio H2/CO = 2, gas space velocity—1000 h−1, temperature—250 °C. The selectivity for the gasoline fraction is 65.2%, and the ratio of branched to linear hydrocarbons (iso/n index) is 2.3. Under the specified technological conditions, an experimental batch of gasoline fraction (1000 cm3) was produced at the pilot plant during 400 h of continuous operation. The main physicochemical and operational parameters of the experimental gasoline fraction of hydrocarbons have been determined. The octane number determined by the research method according to GOST R 52947-2019 is 78.5 units. [ABSTRACT FROM AUTHOR]

Crystal structures of high-temperature t- (LaF3-type) and low-temperature β- (β-YF3-type) modifications of 61(58Ce0.564Gd0.5)F3 – "pseudo61PmF3" near the temperature of a polymorphic transformation (PolTr) (−148 ± 5 °C) were studied by in situ X-ray diffraction (XRD). During the t- → β- "pseudo61PmF3" PolTr (at cooling) anions are ordered in the direction perpendicular to the hexagonal close packing (HCP) layers. This is accompanied by 13% stretching of the t-type crystal lattice in the <010> direction and compression in the <100> (0.8%) and <001> (0.9%) directions. The structural changes in t- and β- "pseudo61PmF3" at heating from −148 to +20 °C represent changes (decrease and increase) in cation–anion bond lengths (BL) without changing the shape of the coordination polyhedron (CP). "Pseudo61PmF3" is a material with giant negative thermal expansion at PolTr (NTE-II). The decrease in volume during the β- → t- "pseudo61PmF3" PolTr (at heating) is 3.8%. [ABSTRACT FROM AUTHOR]

Fast crystallization of the monoclathrochelate cobalt(II) intracomplex [Co(Cl2Gm)3(BAd)2] (where Cl2Gm2− is a dichloroglyoxime dianion and BAd is an adamantylboron capping group, 1), initially obtained by the direct template condensation of the corresponding chelating α-dioximate and cross-linking ligand synthons on the Co2+ ion as a matrix, from benzene or dichloromethane afforded its structural triclinic and hexagonal polymorphs. Its prolonged recrystallization from dichloromethane under air atmosphere and sunlight irradiation unexpectedly gave the crystals of the CoIIICoIICoIII-trinuclear dodecachloro-bis-clathrochelate intracomplex [[CoIII(Cl2Gm)3(BAd)]2CoII] (2), the molecule of which consists of two macrobicyclic frameworks with encapsulated low-spin (LS) Co3+ ions, which are cross-linked by a μ3-bridging Co2+ ion as a bifunctional Lewis-acidic center. The most plausible pathway of such a 1 → 2 transformation is based on the photoinitiated radical oxidation of dichloromethane with air oxygen giving the reactive species. Cobalt(II) monoclathrochelate 1 was found to undergo a temperature-induced spin crossover (SCO) both in its solutions and in the solid state. In spite of the conformational rigidity of the corresponding quasiaromatic diboron-capped tris-α-dioximate framework, the main parameters of this SCO transition (i.e., its completeness and gradual character) are strongly affected by the nature of the used solvent (in the case of its solutions) and by the structural polymorphism of its crystals (in the solid state). In the latter case, the LS state (S = 1/2) of this complex is more thermally stable and, therefore, the cobalt(II)-centered 1/2 → 3/2 SCO is more gradual than that in solutions. [ABSTRACT FROM AUTHOR]

A new 1D-coordination polymer [Co(Piv)2(NH2(CH2)6NH2)]n (1, Piv is Me3CCO2− anion) was obtained, the mononuclear fragments {Co(O2CR)2} within which are linked by μ-bridged molecules of hexamethylenediamine (NH2(CH2)6NH2). For this compound, two different monoclinic C2/c (α-1) and P2/n (β-1) phases were found at room temperature by single-crystal X-ray diffraction analysis, with a similar structure of chains and their packages in unit cells. The low-temperature phase (γ-1) of crystal 1 at 150 K corresponds to the triclinic space group P-1. As the temperature decreases, the structural phase transition (SPT) in the α-1 and β-1 crystals is accompanied by an increase in the crystal packing density caused by the rearrangements of both H-bonds and the nearest ligand environment of the cobalt atom ("octahedral CoN2O4 around the metal center at room temperature" → "pseudo-tetrahedral CoN2O2 at 150 K"). The SPT was confirmed by DSC in the temperature range 210–150 K; when heated above 220 K, anomalies in the behavior of the heat flow are observed, which may be associated with the reversibility of SPT; endo effects are observed up to 300 K. The SPT starts below 200 K. At 100 K, a mixture of phases was found in sample 1: 27% α-1 phase, 61% γ-1 phase. In addition, at 100 K, 12% of the new δ-1 phase was detected, which was identified from the diffraction pattern at 260 K upon subsequent heating: the a,b,c-parameters and unit cell volume are close to the structure parameters of γ-1, and the values of the α,β,γ-angles are significantly different. Further heating leads to a phase transition from δ-1 to α-1, which both coexist at room temperature. According to the DC magnetometry data, during cooling and heating, the χMT(T) curves for 1 form a hysteresis loop with ~110 K, in which the difference in the χMT values reaches 9%. Ab initio calculations of the electronic structure of cobalt(II) in α-1 and γ-1 have been performed. Based on the EPR data at 10 K and the ab initio calculations, the behavior of the χMT(T) curve for 1 was simulated in the temperature range of 2–150 K. It was found that 1 exhibits slow magnetic relaxation in a field of 1000 Oe. [ABSTRACT FROM AUTHOR]