Kinetika i kataliz

В настоящее время единственное специализированное российское периодическое издание, публикующее результаты теоретических и экспериментальных исследований в области гомогенной и гетерогенной кинетики и катализа. Тематика журнала охватывает механизмы и кинетику некаталитических процессов в газовой, жидкой и твердой фазах, фотокатализ, квантово-химические расчеты в области кинетики и катализа, приготовление катализаторов, проблемы их дезактивации, макрокинетику и компьютерное моделирование в области катализа.

Журнал «Кинетика и катализ» входит в Перечень ВАК и систему РИНЦ. Включен в международные базы данных CAPlus, Web of Science, Scopus и др.

Журнал основан в 1960 году.

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Vol 64, No 3 (2023)

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Mechanism and Kinetic Laws of Reactions Determining Flame Propagation, Gas Explosion and Detonation. Review
Azatyan V.V.

It has been established that, contrary to previous ideas chemical processes in the propagation of flame, explosion and detonation of gases, are chain reactions proceeding according to previously unknown laws of non-isothermal chain processes. The characteristic reaction times in deflagration and detonation in the combustion zone are less than a ten-thousandth and a millionth of a second, respectively. The features of the mechanisms and laws that determine such high rates and accelerations of reactions, their extremely strong temperature dependence is revealed. Using kinetic and spectroscopic methods, the decisive role of atoms and radicals, which are formed in concentrations reaching tens of percent of the concentrations of the initial reagents, is shown. Efficient chemical methods for controlling all combustion modes have been developed.

Kinetika i kataliz. 2023;64(3):251-266
pages 251-266 views


On the Nature of the Nonmonotonic Dependence of the Pressure Flame Limits on Temperature CH+ 2OMixtures
Karnaukh A.A., Ivanova A.N.

In the present work, for the first time for stoichiometric methane–oxygen mixtures, two numerical kinetic methods reproduce the nonmonotonic boundary of the “three pressure limits” region obtained by N.N. Semenov’ coworkers experimentally in a wide pressure range ~20–600 Torr. In where take place the llow pressure ignition peninsula, range of parameters, the simulation of self-ignition delays was carried out. In this case, a nonlinear scheme of methane oxidation (150 reactions) was used to calculate ignition delays. According to the linear part of the same scheme (~20 reactions of the methyl peroxide cycle), formulas for the corresponding Jacobi matrix determinant were obtained for the first time, and for each given temperature, from the equation that determines its zero, three pressure roots were found, from which the boundary line of the region, nonmonotonic in pressure, was constructed self-ignition. Satisfactory convergence of the experimental and calculated data is shown both in terms of delay times and in terms of the position of the limits in the P–T space.

Kinetika i kataliz. 2023;64(3):267-273
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Photocatalytic Degradation of Rhodamine B on MOSMicrospheres Prepared by Sodium Dialkyldithiophosphate-Assisted Hydrothermal Synthesis
Ri Y., Kim J., Kim K.

MoS2 microspheres were synthesized via a facile hydrothermal method using (NH4)2MoO4, H2C2O4·2H2O, and sodium dialkyldithiophosphate (NaDDP) as reactants. Herein, NaDDP plays a role of surfactant for the formation of the MoS2 microspheres, unlike other different sulfur sources. The morphology and crystal structure of the MoS2 microspheres were characterized using scanning electron microscope (SEM) and X-ray diffraction (XRD). The prepared MoS2 microspheres were used as a catalyst for photocatalytic degradation of rhodamine B. The effect of the size of the MoS2 microspheres on photocatalytic activity was investigated. For comparison, NaDDP was replaced by thiourea, thioacetamide and L-cysteine. The results indicate that the MoS2 microspheres are spherical, and the diameter of the MoS2 microsphere decreases with increasing concentration of oxalic acid in the reactants. The MoS2 microspheres have hexagonal 2H-MoS2 structure and preferentially grow along the (002) plane. In addition, it is found that when the concentration of oxalic acid is 0.075 mol/L, the best photocatalytic efficiency is 91.3% within irradiation time of 120 min and the reaction rate constant is 0.163 min–1. The photocatalytic activity of MoS2 synthesized from four sulfur sources can be arranged in the following order: NaDDP > thioacetamide > L-cysteine > thiourea.

Kinetika i kataliz. 2023;64(3):274-275
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Novel Two-Stage Method of Preparing Graphitic Carbon Nitride Doped by Chlorine for Photocatalytic Hydrogen Evolution and Photocurrent Generation
Zhurenok A.V., Markovskaya D.V., Potapenko K.O., Sidorenko N.D., Cherepanova S.V., Saraev A.A., Gerasimov E.Y., Kozlova E.A.

In this work graphitic carbon nitride doped by chlorine was prepared by a two-stage technique at first. At the first stage melamine was hydrothermally treated with glucose, at the second stage the mixture of as-prepared melamine with ammonium chloride was calcined. The obtained samples were investigated by the set of methods: X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), diffuse reflectance spectroscopy, photoelectrochemical methods. All prepared photocatalysts was tested in the reaction of photocatalytic hydrogen production from basic solutions of triethanolamine. It was shown that the highest values of the catalytic activity and short-circuit current density were obtained over the photocatalyst preparing by calcination of the mixture containing 30% ammonium chloride and 70% melamine. The highest value of the catalytic activity was 1332 μmol h–1 g–1 and was more than the catalytic activity of carbon nitride preparing by the melamine calcination without another treatment in 22 times.

Kinetika i kataliz. 2023;64(3):276-286
pages 276-286 views
Development and Investigation of Carbon-Mineral Catalyst Based on Natural Clay and Tire Crush for Oxidative Decomposition of Nonionic Surfactants by Hydrogen Peroxide in Wastewater
Fidchenko M.M., Alekhina M.B., Beznosyuk A.N., Varnavskaya A.D., Mishchenko E.V.

Samples of a carbon-mineral catalyst based on natural clay and tire crumb for the reaction of oxidative decomposition of nonionic surfactants by hydrogen peroxide in wastewater have been developed and studied. The iron content in the samples varied in the range of 2.3–3.9 wt %. The effect of sample pyrolysis temperature in the range of 350–800°С on characteristics, the number and type of acid sites on the surface, and the ζ (zeta) potential of colloidal systems based on prepared samples was studied. Using model solutions under static and dynamic conditions, the effect of sample pyrolysis temperature on catalytic properties in the reaction of oxidative decomposition of H2O2 and nonionic surfactant (NS) nonoxynols N-9 by hydrogen peroxide was studied. The best result in the oxidation of nonoxynols N-9 with hydrogen peroxide was obtained in the presence of a carbon-mineral catalyst sample calcined at 650°C.

Kinetika i kataliz. 2023;64(3):287-297
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Kinetics of Catalytic Oxidation of Oleic Acid Methyl Ester
Yhshchenko D.Y., Pai Z.P., Uchenova U.V., Khlebnikova T.B.

The results of studying the kinetics of the reaction of catalytic oxidation of oleic acid methyl ester with hydrogen peroxide in a two-phase system (aqueous phase-organic phase) in the presence of a bifunctional catalyst of the composition [(Octn)3NMe]3{PO4[WO(O2)2]4} are presented. For the selected reaction conditions, the first orders of catalyst, substrate and oxidizer are established. The value of the activation energy for the temperature range 313–353 K is 47 ± 3 kJ/mol, and the pre-exponential multiplier is (6.0 ± 0.3) × 107 L2 mol–2 min–1.

Kinetika i kataliz. 2023;64(3):298-304
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Kinetic Investigation on Selective COHydrogenation to Formic Acid over Rhodium Hydrotalcite (Rh-HT) Catalyst
Maru M.S., Ram S., Shukla R.S.

A heterogeneous catalyst, rhodium hydrotalcite (Rh-HT), was synthesized, characterized, and explored for kinetic studies for the hydrogenation of CO2 to formic acid using molecular hydrogen in an autoclave. The catalyst was efficient for the selective formation of formic acid at a moderate temperature with up to 5 catalytic cycles without any significant loss in catalytic activity. The detailed kinetic investigations were performed by determining the rate of formic acid formation as a function of time, catalyst amount, total pressure, partial pressure of CO2, partial pressure of H2, reaction volume, v/v ratio of the mixed solvent of methanol and water, agitation speed, and temperature in a wide range of variation. The rates were found to be dependent on all these parameters. The formic acid formation rate followed the first-order kinetics with respect to the partial pressures of CO2 and H2, and catalyst amount. The best reaction conditions obtained from the kinetic parametric optimisation were, 50 bar total pressure (1/1 p/p, CO2 and H2); 60°C temperature; a mixture of methanol:water solvent (5/1 v/v, 60 mL); 24 h time; and 500 rpm agitation speed to get a TON of 15840 for formic acid with no additional base. The thermodynamic performance of the heterogeneous catalyst Rh-HT was appreciably associated with highly negative entropy. The performance of the catalyst was effectively enhanced by the mixture of water and methanol as a solvent. The mechanistic routes for CO2 hydrogenation to formic acid are proposed and discussed based on the kinetic and experimental observations involving the role of the molecular effect of water used in the solvent.

Kinetika i kataliz. 2023;64(3):305-306
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Stereoselectivity of Acetylene Hydrochlorination over Supported PdCl/С Catalysts
Krasnyakova T.V., Nikitenko D.V., Kobets K.D., Krasniakova I.O., Gogilchin A.S., Bugaev A.L., Mitchenko S.A.

The products of catalytic hydrochlorination of acetylene-D2 over palladium chloride complexes supported on activated carbon are a mixture of vinyl chloride stereoisomers resulting from syn- and anti-addition of the hydrogen chloride molecule to the triple bond. The reaction is accompanied by isomerization of primary trans-vinyl chloride into its cis-stereoisomer, but the characteristic isomerization times exceed significantly the duration of acetylene hydrochlorination. This fact allowed us to estimate the portion of products formed exclusively during the catalytic reaction, the difference in the effective activation energies of the syn- and anti-addition routes (~21 kJ/mol), and to demonstrate a monotonic increase in the part of the syn-addition product with increasing mass loading ω of the active metal, reaching saturation at ω > 2 wt %.

Kinetika i kataliz. 2023;64(3):307-316
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On the Possibility of Thermokinetic Oscillations in the Reaction of Methane Oxidation on Nickel
Peskov N.V., Slinko M.M.

The paper demonstrates the possibility of occurrence of thermokinetic oscillations during the methane oxidation on a nickel industrial catalyst at real values of the parameters. It is shown that reaction rate oscillations can originate under the conditions of short contact times and in the region where periodic oxidation–reduction processes do not occur. The origin of these thermokinetic oscillations is the periodic blocking of the surface with carbon and its cleaning by removing carbon from the catalyst surface.

Kinetika i kataliz. 2023;64(3):317-325
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Studying the Properties of Molecular Sites Produced from Gels Containing Layered 2D Silicoalumophosphates with Different SiO/AlO Ratio
Agliullin M.R., Serebrennikov D.V., Khalilov L.M., Fayzullina Z.R., Pavlova I.N., Kutepov B.I.

Crystallization of molecular SAPO-41 sieves from gels containing layered 2D silicoaluminophosphates with various SiO2/Al2O3 molar ratios (from 0.1 to 0.3). The effect of the presence of layered phases in gels on the chemical and phase composition, acid properties, and the characteristics of the porous structure of their crystallization products has been established. A method for the synthesis of SAPO-41 of high phase purity and degree of crystallinity is proposed. The catalytic properties in the hydromeasurement of n-hexadecane prepared on the basis of the obtained molecular sieves of Pt-containing catalytic systems have been studied.

Kinetika i kataliz. 2023;64(3):326-335
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Stabilization of a Carbon Support by Surface Oxygen with Respect to Nitrogen Dioxide in the Pd/HOPG Model System
Smirnov M.Y., Kalinkin A.V., Bukhtiyarov V.I.

X-ray photoelectron spectroscopy (XPS) method has been used to study the effect of oxygen on the surface of a carbon support on the result of NO2 interaction with model systems prepared by evaporation of palladium on highly oriented pyrolytic graphite (HOPG). For Pd/HOPG samples with an atomic ratio [O]/[C] ≤ 0.0035, graphite oxidized with the destruction of its structure to a depth of 10–15 graphene layers. In this case, palladium particles remained in the metallic state and penetrated into the subsurface layer of the support due to the deep oxidation of the adjacent carbon atoms. At the atomic ratio [O]/[C] ≈ 0.01–0.02, the result of the interaction changed dramatically. In this case, the HOPG remained stable, and the palladium particles were oxidized to form an oxide. This finding explained the high stability of supported palladium catalysts prepared on Sibunit carbon supports in reactions of oxidation catalysis.

Kinetika i kataliz. 2023;64(3):336-344
pages 336-344 views

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