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Journal Cover Kinetics and Catalysis
  [SJR: 0.317]   [H-I: 23]   [3 followers]  Follow
   Hybrid Journal Hybrid journal (It can contain Open Access articles)
   ISSN (Print) 1608-3210 - ISSN (Online) 0023-1584
   Published by Springer-Verlag Homepage  [2335 journals]
  • Inhibition of the reaction between hydrogen and oxygen by multiatomic gas
           admixtures behind the incident shock wave front
    • Authors: O. V. Skrebkov; S. S. Kostenko
      Pages: 1 - 8
      Abstract: The inhibiting effect of multiatomic gases has been investigated by numerical simulation of hydrogen oxidation with account taken of the nonequilibrium state of the initial components, intermediates, and reaction products behind the shock wave in the framework of a vibrationally nonequilibrated model. The central feature of the model is successively taking into account the vibrational disequilibrium of the HO2 radical as the most important intermediate in the chain branching process. The inhibiting effect can be explained by the influence of the multiatomic gases on the rate of the vibrational relaxation of the vibrationally excited HO2 radical resulting from the reaction. Methane, tetrafluoromethane, fluoromethane, difluoromethane, chlorofluoromethane, formaldehyde, ethane, hexafluoroethane, ethylene, tetrafluoroethylene, and propane have been considered as inhibitory admixtures.
      PubDate: 2017-01-01
      DOI: 10.1134/s0023158417010098
      Issue No: Vol. 58, No. 1 (2017)
  • Reactivity of cycloalkanes in hydrogen abstraction with different
    • Authors: B. E. Krisyuk; E. A. Mamin; A. A. Popov
      Pages: 9 - 14
      Abstract: The reactions of some acceptors (∙CH3, ∙OOH, ∙CCl3, O3, and Br∙) with saturated cyclic hydrocarbons, viz., cyclohexane, cycloheptane, and cyclooctane were studied by the DFT methods based on B3LYP and PBE0 functionals, the method based on the double hybrid functional B2PLYP, a combined ONIOM approach (CCSD:B3LYP)) and the coupled-cluster method (CCSD) using the 6-31+G**, aug-cc-pVDZ, Midi-X, and SVP basis sets. A specific feature of these reactions is that their rates depend on the excess ring energy, although no ring opening occurs in all cases.
      PubDate: 2017-01-01
      DOI: 10.1134/s0023158417010050
      Issue No: Vol. 58, No. 1 (2017)
  • Dissociation energies of O–H bonds in alkylseleno- and
           alkyltelluro-substituted phenols
    • Authors: T. G. Denisova; E. T. Denisov
      Pages: 15 - 23
      Abstract: The O−H bond dissociation energy (D O−H) has been determined for eight alkylseleno-substituted phenols, one alkyltelluro-substituted phenol, and one alkyltelluro-substituted pyridinol. D O−H has been estimated by the intersecting-parabolas method from kinetic data using five reference compounds: α-tocopherol (D O−H = 330.0 kJ/mol), 3,5-di-tert-butyl-4-methoxyphenol (D O−H = 347.6 kJ/mol), 4-methylphenol (D O−H = 361.6 kJ/mol), 2,6-di-tert-butyl-4-methylthiophenol (D O−H = 336.3 kJ/mol), and 2,6-di-ter-tbutyl-4-methylphenol (D O−H = 338.0 kJ/mol). The following D O−H values (kJ/mol) have been obtained: 335.9 for 2,5,7,8-tetramethyl-2-phytyl-6-hydroxy-3,4-dihydro-2H-1-benzoselenopyran, 342.6 for 2-methyl-5-hydroxy-2,3-dihydrobenzoselenophene, 333.5 for 2,4,6,7-tetramethyl-5-hydroxy-2,3-dihydrobenzoselenophene, 339.4 for 2-tert-butyl-4-methoxy-6-octylselenophenol, 357.9 for dodecyl 3-(4-hydroxyphenyl) propyl selenide, 348.5 for dodecyl 3-(3,5-dimethyl-4-hydroxyphenyl)propyl selenide, 350.9 for dodecyl 3-(3-tert-butyl-4-hydroxyphenyl)propyl selenide, 338.0 for dodecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propyl selenide, 343.0 for 2,6-di-tert-butyl-4-(tellurobutyl-4′-phenoxy)phenol, and 338.8 for 6-octyltelluro-3-pyridinol. The stabilization energies of phenoxyl radicals containing R substituents (X = O, S, Se, Te) have been compared.
      PubDate: 2017-01-01
      DOI: 10.1134/s0023158417010013
      Issue No: Vol. 58, No. 1 (2017)
  • Ion-exchange resin catalysts in the liquid-phase hydrazinolysis of
           cinnamic acid
    • Authors: S. A. Dzhumadullaeva; A. B. Baeshov
      Pages: 24 - 27
      Abstract: The catalytic activity of a synthetic ion-exchange resins has been studied in the reaction of cinnamic acid with hydrazine (aqueous medium, 363 K, 1.0–2.5 h) yielding the corresponding hydrazide. Efficient catalysts for the process are the anion-exchange resins AV-17-8 and AN-31. The modifying effect of the substrate—hydrazine hydrate—on the catalytic properties of the ion-exchange systems has been demonstrated. On the basis of IR spectroscopic studies, a plausible process mechanism was suggested. It involves polymer-bound quaternary ammonium ions of the anion exchanger.
      PubDate: 2017-01-01
      DOI: 10.1134/s0023158417010025
      Issue No: Vol. 58, No. 1 (2017)
  • Oxidative desulfurization of thiophene derivatives with H 2 O 2 in the
           presence of catalysts based on MoO 3 /Al 2 O 3 under mild conditions
    • Authors: Y. Shen; X. Lu; X. Ma; J. He; D. Zhang; H. Zhan; Q. Xia
      Pages: 28 - 33
      Abstract: The catalysts based on MoO3/Al2O3 were synthesized and tested using aqueous hydrogen peroxide as the oxidant in the oxidative desulfurization of thiophene, benzothiophene (BT) and dibenzothiophene (DBT) into the corresponding sulfones. Among catalysts tested, 15%(MoO3–WO3)/Al2O3 prepared by a conventional impregnation method was considerably active for the oxidation of thiophene, BT and DBT, which could achieve higher than 99.2% conversions at lower reaction temperature (≤338 K). The use of hexadecyltrimethyl ammonium bromide as the phase-transfer reagent in small amounts could promote the reaction efficiently.
      PubDate: 2017-01-01
      DOI: 10.1134/s0023158417010086
      Issue No: Vol. 58, No. 1 (2017)
  • Factors determining the chemoselectivity of phosphorus-modified palladium
           catalysts in the hydrogenation of chloronitrobenzenes
    • Authors: N. I. Skripov; L. B. Belykh; T. P. Sterenchuk; V. V. Akimov; V. L. Tauson; F. K. Schmidt
      Pages: 34 - 45
      Abstract: The precursor nature effect on the state of the Pd–P surface layer in palladium catalysts and on their properties in the liquid-phase hydrogenation of chloronitrobenzenes under mild conditions has been investigated. A general feature of the Pd–P-containing nanoparticles obtained from different precursors and white phosphorus at P/Pd = 0.3 (PdCl2 precursor) and 0.7 (Pd(acac)2 precursor) is that their surface contains palladium in phosphide form (BE(Pd3d 5/2) = 336.2 eV and BE(Р2р) = 128.9 eV) and Pd(0) clusters (BE(Pd3d5/2) = 335.7 eV). Factors having an effect on the chemoselectivity of the palladium catalysts in chloronitrobenzenes hydrogenation are considered, including the formation of small palladium clusters responsible for hydrogenation under mild conditions.
      PubDate: 2017-01-01
      DOI: 10.1134/s0023158417010104
      Issue No: Vol. 58, No. 1 (2017)
  • Mechanisms of the stabilization of a molybdenum epoxidation catalyst by
           nitrogen-containing compounds
    • Authors: G. G. Elimanova; N. N. Batyrshin; Kh. E. Kharlampidi
      Pages: 46 - 50
      Abstract: Nitrogen-containing compounds have been studied as stabilizing additives for a complex molybdenum catalyst for propylene epoxidation with ethylbenzene hydroperoxide. Introducing the additives increases the half-life period by a factor of 10–14. The effective constants and rates of the decomposition of the catalytic complex in the presence of stabilizing agents have been calculated. Two possible mechanisms of the action of the nitrogen-containing additives have been suggested.
      PubDate: 2017-01-01
      DOI: 10.1134/s0023158417010037
      Issue No: Vol. 58, No. 1 (2017)
  • Preparation method effect on the physicochemical and catalytic properties
           of a methane dehydroaromatization catalyst
    • Authors: O. V. Sedel’nikova; A. A. Stepanov; V. I. Zaikovskii; L. L. Korobitsyna; A. V. Vosmerikov
      Pages: 51 - 57
      Abstract: The molybdenum precursor effect on the physicochemical properties of the Мо/ZSM-5 catalyst and on its catalytic properties in nonoxidative methane conversion into aromatic hydrocarbons has been investigated. The textural characteristics of molybdenum catalysts have been determined by low-temperature nitrogen adsorption, and their acidity has been measured by temperature-programmed ammonia desorption. The microstructure and composition of Mo/ZSM-5 samples have been determined by high-resolution transmission electron microscopy and energy-dispersive X-ray spectroscopy. The activity and on-stream stability of the Мо-containing zeolite catalyst in the nonoxidative conversion of methane depend on the type of molybdenum compound that was used in catalyst preparation.
      PubDate: 2017-01-01
      DOI: 10.1134/s0023158417010074
      Issue No: Vol. 58, No. 1 (2017)
  • Effect of the nature of sulfur compounds on their reactivity in the
           oxidative desulfurization of hydrocarbon fuels with oxygen over a modified
           CuZnAlO catalyst
    • Authors: S. A. Yashnik; A. V. Salnikov; M. A. Kerzhentsev; A. A. Saraev; V. V. Kaichev; L. M. Khitsova; Z. R. Ismagilov; J. Yamin; O. R. Koseoglu
      Pages: 58 - 72
      Abstract: The reactivity of thiophene, dibenzothiophene (DBT), and 4,6-dimethyldibenzothiophene (4,6-DMDBT), which are the representatives of the main classes of sulfur compounds that are the constituents of diesel fractions, was studied in the course of their oxidative desulfurization with oxygen on a CuO/ZnO/Al2O3 catalyst modified with boron and molybdenum additives. At T ≥ 375°C, the reactivity increased in the order thiophene < DBT < 4,6-DMDBT. The degree of sulfur removal in the form of SO2 from hydrocarbon fuel, which was simulated by a solution of 4,6-DMDBT in toluene, was 80%. Under the assumption of a first order reaction with respect to sulfur compound and oxygen, the apparent activation energies of the test processes were calculated. An attempt was made to reveal the role of the adsorption of sulfur compounds in the overall process of oxidative desulfurization with the use of X-ray diffraction analysis, X-ray photoelectron spectroscopy, and differential thermal and thermogravimetric analysis with the massspectrometric monitoring of gas phase composition.
      PubDate: 2017-01-01
      DOI: 10.1134/s0023158417010128
      Issue No: Vol. 58, No. 1 (2017)
  • New bimetallic Mo 2 C–WC/Al 2 O 3 membrane catalysts in the dry
           reforming of methane
    • Authors: V. R. Kislov; V. V. Skudin; A. Adamu
      Pages: 73 - 80
      Abstract: Bimetallic membrane catalysts based on the Mo2C–WC binary carbides were obtained. Their structural characteristics and catalytic properties in a reaction of dry reforming of methane were compared with those of monocarbide catalysts. The advantage of the use of the mixed carbide catalysts was established.
      PubDate: 2017-01-01
      DOI: 10.1134/s0023158417010049
      Issue No: Vol. 58, No. 1 (2017)
  • Industrial catalyst for the selective Fischer–Tropsch synthesis of
           long-chain hydrocarbons
    • Authors: A. P. Savost’yanov; R. E. Yakovenko; G. B. Narochnyi; V. G. Bakun; S. I. Sulima; E. S. Yakuba; S. A. Mitchenko
      Pages: 81 - 91
      Abstract: The results of development of an industrial supported cobalt–silica gel catalyst for the Fischer–Tropsch synthesis are reported. The studies included the selection of a support and the determination of an optimum active component content, a calcination temperature, and the effect of doping with aluminum oxide on the physicochemical and catalytic properties of the Co–SiO2 system. The catalyst samples were characterized by a set of physicochemical methods. The on-stream stability of the supported cobalt–silica gel catalyst was tested in the continuous mode for 1000 h. In the course of the entire test cycle, the catalyst exhibited stable operation under varied synthesis temperature and gas space velocity, and it can be recommended for industrial applications. The experimental results were used for the preparation of a pilot batch of the catalyst.
      PubDate: 2017-01-01
      DOI: 10.1134/s0023158417010062
      Issue No: Vol. 58, No. 1 (2017)
  • Dissolution of oxygen in polycrystalline palladium at $${P_{{O_2}}}$$ P O
           2 = 100 Pa and temperatures of 500 to 950 K
    • Authors: E. A. Suprun; A. N. Salanov
      Pages: 92 - 103
      Abstract: The dissolution of oxygen in polycrystalline palladium Pd(poly) at an O2 pressure of 100 Pa and temperatures of 500–950 K has been investigated by temperature-programmed desorption. At 500 K, the process yields a surface palladium film that includes an oxide-like reconstructed structure on a rarefied metal surface layer. At this temperature, palladium sorbs ~2 monolayers (ML) of oxygen. At 600–800 K, palladium dissolves up to ~140 ML of oxygen as a result of O2 chemisorption on the surface of the oxide film, penetration of Oads atoms under the oxide film, and their diffusion into the metal bulk. The dependence of the amount of oxygen sorbed by Pd(poly) (n) on the time of exposure to an O2 atmosphere is described by a nearparabolic function, n = atb, indicating that oxygen atoms diffuse in the metal lattice. The activation energy of this diffusion, Е dif, is ~83.5 kJ/mol. At high temperatures (800–950 K), palladium sorbs much less oxygen (≤10 ML). This is due to the complete decomposition of the surface oxide film, a process that markedly hampers the insertion of Oads atoms under the surface layer of the metal.
      PubDate: 2017-01-01
      DOI: 10.1134/s0023158417010116
      Issue No: Vol. 58, No. 1 (2017)
  • Inhibition of the photoinduced ignition of chloromethane–chlorine
           mixtures by oxygen
    • Authors: I. R. Begishev; A. K. Belikov; I. S. Nikitin
      Pages: 738 - 741
      Abstract: The introduction of small amounts of oxygen inhibits the photoinduced ignition of chloromethane–chlorine mixtures. This is accompanied by an increase in the induction period and a decrease in the degree of heating of the reaction mixture. After the consumption of the entire inhibitor, the photochlorination reaction takes place again in the thermal explosion regime but with a lower degree of heating. In the dependence of the mixture temperature on the oxygen concentration, criticality is not pronounced. With an increasing concentration of oxygen, its effect on the induction period weakens.
      PubDate: 2016-11-01
      DOI: 10.1134/s002315841606001x
      Issue No: Vol. 57, No. 6 (2016)
  • Mechanism of 5-amino-6-methyluracil-inhibited oxidation of organic
    • Authors: R. A. Nasibullina; L. R. Yakupova; R. L. Safiullin
      Pages: 758 - 767
      Abstract: Based on experimental and theoretical data obtained in the mechanism study of the 5-amino-6-methyluracil-inhibited radical chain oxidation of 1,4-dioxane, a scheme for the process is proposed. A kinetic analysis of the scheme has been performed to obtain an equation describing the regularities of oxygen consumption that agree with the experimental data and provide evidence in favor of the chain consumption of the inhibitor under certain conditions. The composition of resulting products confirms the proposed mechanism.
      PubDate: 2016-11-01
      DOI: 10.1134/s0023158416060100
      Issue No: Vol. 57, No. 6 (2016)
  • Hybridized advanced oxidation processes involving UV/H 2 O 2 /S 2 O 8 2-
           for photooxidative removal of p -nitrophenol in an annular continuous-flow
    • Authors: Morteza Mohammadzadeh; Mohammad A. Behnajady; Hamed Eskandarloo
      Pages: 768 - 775
      Abstract: In this paper, photooxidative removal of p-nitrophenol (PNP) as a model organic pollutant was investigated in the presence of UV/inorganic oxidants system in an annular continuous-flow photoreactor. The aim of this study was to evaluate the photooxidative efficiency of hybrid oxidant system including persulfate (UV/H2O2/S2O 8 2- ) and hydrogen peroxide (H2O2), under UV–C light irradiation. The effects of operational variables including UV/H2O2/S2O 8 2- and H2O2 concentrations, the initial PNP concentration, and residence time on the removal efficiency of UV/H2O2/H2O2/S2O 8 2- system were studied. It was found that the operational variables affected the removal efficiency of UV/H2O2/H2O2/S2O 8 2- system. Operating conditions were optimized using response surface methodology (RSM). Simulation approach showed that the predicted values of removal efficiency are in good agreement with the experimental results with a correlation coefficient (R 2) of 0.95. Optimization results showed that the maximum degree of removal (98%) was achieved by using the UV/H2O2/H2O2/S2O 8 2- system under the following operation conditions: concentration of H2O2 = 10 mmol/L, concentration of UV/H2O2/S2O 8 2- = 10 mmol/L, initial concentration of PNP = 35 mg/L, and residence time = 8 min. The obtained results clearly demonstrated that RSM is one of the useful and cost-effective methods for modeling and optimizing the efficiency of UV/H2O2/UV/H2O2/S2O 8 2- system.
      PubDate: 2016-11-01
      DOI: 10.1134/s0023158416060021
      Issue No: Vol. 57, No. 6 (2016)
  • Role of anionic vacancies in lithium fluoride in the catalytic oxidation
           of carbon monoxide on the surface of the Au/LiF/Mo(110) system
    • Authors: I. V. Silaev; S. A. Khubezhov; I. V. Tvauri; G. S. Grigorkina; A. G. Kaloeva; O. G. Ashkhotov; D. Sekiba; S. Ogura; K. Fukutani; T. T. Magkoev
      Pages: 797 - 802
      Abstract: The oxidation of carbon monoxide molecules on the surface of gold nanoclusters formed on a lithium fluoride film has been investigated by IR spectroscopy and temperature-programed reaction. The CO oxidation rate is much higher in the case of gold clusters produced on the surface of a LiF film enriched with anionic vacancies (F-centers). This is due to the fact that the gold clusters bonded to F-centers of the substrate differ in electronic state from the clusters that are not bonded to F-centers.
      PubDate: 2016-11-01
      DOI: 10.1134/s0023158416060148
      Issue No: Vol. 57, No. 6 (2016)
  • Effect of the ligand nature in cobalt complexes on the selectivity of the
           reaction of carbon dioxide and propylene oxide
    • Authors: O. M. Chukanova; G. P. Belov
      Pages: 821 - 825
      Abstract: The reaction of carbon dioxide with propylene oxide in the presence of the (salen)CoCl or (TPP)CoCl (salen = bis(3,5-di-tert-butyl-salicylidene)-1,2-diaminocyclohexane, TPP = 5,10,15,20-tetraphenylporphyrin) catalyst and the PPNCl (bis(triphenylphosphine)iminium chloride) cocatalyst has been carried out at 20–60°С and a СО2 pressure of 0.6 MPa to investigate the effect of the ligand nature on the reaction rate and selectivity. The change in the reaction rate and selectivity in relation to the temperature and cocatalyst/catalyst ratio has been studied. The activation energy of the copolymerization of СО2 with propylene oxide catalyzed by the (salen)CoCl complex have been obtained.
      PubDate: 2016-11-01
      DOI: 10.1134/s0023158416050074
      Issue No: Vol. 57, No. 6 (2016)
  • Oxidation of a platinum foil with nitrogen dioxide
    • Authors: A. V. Kalinkin; M. Yu. Smirnov; V. I. Bukhtiyarov
      Pages: 826 - 830
      Abstract: The oxidation of a polycrystalline platinum foil by nitrogen dioxide at an NO2 pressures of 10–6–10–4 mbar and a temperature of 525 K has been investigated by X-ray photoelectron spectroscopy (XPS). Under these conditions, the platinum oxides PtO and Pt3O4 form on the foil surface. A comparison between the data obtained in this study and the data on the oxidation of platinum nanoparticles suggests a hypothesis as to the causes of the size effect in the oxidation of NO over platinum catalysts.
      PubDate: 2016-11-01
      DOI: 10.1134/s0023158416060069
      Issue No: Vol. 57, No. 6 (2016)
  • Catalysts with platinum–palladium nanoparticles on polymer matrix
    • Authors: M. V. Lebedeva; N. A. Yashtulov; V. R. Flid
      Pages: 847 - 852
      Abstract: The platinum–palladium/Nafion metal–polymer nanocomposites were synthesized by the chemical reduction of ions in the aqueous organic solutions of inverted microemulsions. The functional characteristics of the nanocomposites were studied by cyclic voltammetry, atomic force microscopy, and scanning electron microscopy. The nanocatalysts obtained exhibited high activity in the reactions of oxygen reduction and hydrogen oxidation. The influence of synthesis conditions on the catalytic activity of the metal–polymer nanocomposites was studied.
      PubDate: 2016-11-01
      DOI: 10.1134/s0023158416060070
      Issue No: Vol. 57, No. 6 (2016)
  • Formation of Pd–Ag nanoparticles in supported catalysts based on the
           heterobimetallic complex PdAg 2 (OAc) 4 (HOAc) 4
    • Authors: A. V. Rassolov; P. V. Markov; G. O. Bragina; G. N. Baeva; D. S. Krivoruchenko; I. S. Mashkovskii; I. A. Yakushev; M. N. Vargaftik; A. Yu. Stakheev
      Pages: 859 - 865
      Abstract: The formation of Pd–Ag nanoparticles deposited from the heterobimetallic acetate complex PdAg2(OAc)4(HOAc)4 on α-Al2O3, γ-Al2O3, and MgAl2O4 has been investigated by high-resolution trans-mission electron microscopy, temperature-programmed reduction, and IR spectroscopy of adsorbed CO. The reduction of PdAg2(OAc)4(HOAc)4 supported on γ-Al2O3 and MgAl2O4 takes place in two steps (at 15–245 and 290–550°C) and yields Pd–Ag particles whose average size is 6–7 nm. The reduction of the Pd–Ag catalyst supported on α-Al2O3 occurs in a much narrower temperature range (15–200°C) and yields larger nanoparticles (~10–20 nm). The formation of Pd–Ag alloy nanoparticles in all of the samples is demonstrated by IR spectroscopy of adsorbed CO, which indicates a marked weakening of the absorption band of the bridged form of adsorbed carbon monoxide and a >30-cm–1 bathochromic shift of the linear adsorbed CO band. IR spectroscopic data for PdAg2/α-Al2O3 suggest that Pd in this sample occurs as isolated atoms on the surface of bimetallic nanoparticles, as is indicated by the almost complete absence of bridged adsorbed CO bands and by a significant weakening of the Pd–CO bond relative to the same bond in the bimetallic samples based on γ-Al2O3 and MgAl2O4 and in the monometallic reference sample Pd/γ-Al2O3.
      PubDate: 2016-11-01
      DOI: 10.1134/s0023158416060112
      Issue No: Vol. 57, No. 6 (2016)
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Heriot-Watt University
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