Эволюция состава анолита при окислительном электролизе сернокислого раствора бромида натрия / М. М. Петров, П. А. Локтионов, Д. В. Конев и др. // Электрохимия. — 2019. — Т. 55. — С. 95–105. [ DOI ]
A hydrogen-bromate flow battery for air-deficient environments / A. D. Modestov, D. V. Konev, O. V. Tripachev et al. // ENERGY TECHNOLOGY. — 2018. — Vol. 6, no. 2. — P. 242–245. [ DOI ]
Vorotyntsev M. A., Rubashkin A. A., Antipov A. E. A new approach in the theory of spatially-restricted nonlocal dielectric media // Russian Journal of Electrochemistry. — 2018. — Vol. 54, no. 11. — P. 879–885. [ DOI ]
Antipov A. E., Vorotyntsev M. A. Bromate anion reduction at rotating disk electrode in steady state under excess of protons: Numerical solution of the convective diffusion equations at equal diffusion coefficients of components // Russian Journal of Electrochemistry. — 2018. — Vol. 54, no. 1. — P. 62–69. [ DOI ]
Bromate reaction on a rotating disc electrode: A new method of obtaining approximate analytical solutions for stationary regime / M. A. Vorotyntsev, A. E. Antipov, M. M. Petrov et al. // Doklady Chemistry. — 2018. — Vol. 483, no. 1. — P. 256–260. [ DOI ]
Vorotyntsev M. A., Antipov A. E. Bromate electroreduction from acidic solution at rotating disc electrode. theoretical study of the steady-state convective-diffusion transport for excess of bromate ions compared to protons // Electrochimica Acta. — 2018. — Vol. 261. — P. 113–126. [ DOI ]
Bromate electroreduction from sulfuric acid solution at rotating disk electrode: Experimental study / A. D. Modestov, D. V. Konev, A. E. Antipov et al. // Electrochimica Acta. — 2018. — Vol. 259, no. 1. — P. 655–663. Our recent theoretical analysis of the bromate reduction from acidic media at rotating disk electrode (RDE) under steady-state conditions gave astonishing predictions for the current at the plateau of the voltammogram (called “the maximal current”, jmax) which deviated cardinally from those for the previously known mechanisms of electrochemical processes. Because of the non-electroactivity of the bromate anion itself, its transformation (without an added catalyst) can only take place owing to the redox cycle composed of the rapid reduction of bromine species (which are always present in low amounts inside strongly acidic solutions of bromates) into bromide ions at the electrode and of the comproportionation reaction between bromate and bromide ions inside the solution phase which regenerates bromine molecules. According to this theory, owing to the autocatalytic features of this mechanism the dependence of the maximal current density, jmax, on the RDE revolution frequency, f, is complicated. In particular, it includes a range of relatively low frequencies where the maximal current can exceed the bromate diffusion-limited one, even for tracer amounts of bromine in the bulk solution. Another surprising conclusion of the theory is the existence of an intermediate range of frequencies (“anomalous region”) where the maximal current increases if the rotation frequency diminishes, i.e. for the weaker agitation intensity. This study presents the first experimental verification of these predictions for a series of bromate solutions of various concentrations in 2 M sulfuric acid. Qualitative analysis of these experimental data has confirmed the principal theoretical expectations, first of all the existence of the anomalous region of frequencies. At the same time it has been found that the previously published theoretical model based on the literature data for the parameters of the system (diffusion coefficients of solution components, rate constant of the comproportionation reaction, etc.) corresponding to dilute solutions is not able to provide a quantitative interpretation of experimental data. An advanced variant of the theory has been proposed that takes into account the dependence of these parameters on the solution composition, first of all on the effect of the acid concentration. Comparison of predictions of this model with experimental data has shown their quantitative agreement, i.e. the simulated plots for the dependence, jmax(f), turned out to be close to experimental data within the whole range of frequencies available experimentally. This result represents an unambiguous proof of validity both of the principles of the underlying theory of this process and of the predictions derived within its framework. [ DOI ]
Antipov A. E., Vorotyntsev M. A. Maximum current density in the reduction of the bromate anion on a rotating disk electrode: Asymptotic behavior at large thicknesses of the diffusion layer // Russian Journal of Electrochemistry. — 2018. — Vol. 54, no. 2. — P. 186–194. [ DOI ]
Vorotyntsev M. A., Аntipov A. E. Novel procedure towards approximate analytical description of bromate-anion reduction at rotating disk electrode under steady-state transport conditions // Electrochimica Acta. — 2018. — Vol. 289. — P. 272–282. [ DOI ]
Surprising dependence of the current density of bromate electroreduction on the microelectrode radius as manifestation of the autocatalytic redox-cycle (ec″) reaction mechanism / D. V. Konev, A. E. Antipov, M. M. Petrov et al. // Electrochemistry Communications. — 2018. — Vol. 86. — P. 76–79. Bromate reduction from strongly acidic solutions under steady-state conditions in the presence of a very small amount of bromine has been studied voltammetrically at disk microelectrodes of various radii. In conformity with theoretical predictions the intensity of the average current density depends on the electrode size in a non-monotonous manner, passing through a maximum for a certain radius. This behavior is a direct consequence of the autocatalytic character of this process where the non-electroactive bromate anion is reduced owing to the catalytic cycle based on the bromine/bromide redox-mediator couple. The experimentally observed dependence of the maximal current density, jmax, on the inverse disc radius, 1/r0, for electrodes of larger sizes approaches a straight line corresponding to the “strong current limit”, which exceeds the diffusion-limited current density for bromate ion. [ DOI ]
Vorotyntsev M. A., Antipov А. Е., Konev D. V. Bromate anion reduction: novel autocatalytic (ec") mechanism of electrochemical processes. its implication for redox flow batteries of high energy and power densities // Pure and Applied Chemistry. — 2017. — Vol. 89, no. 10. — P. 1429–1448. [ DOI ]
Vorotyntsev M. A., Antipov А. Е. Bromate electroreduction from acidic solution at rotating disk electrode. theory of steady-state convective-diffusion transport // Electrochimica Acta. — 2017. — Vol. 246. — P. 1217–1229. [ DOI ]
Vorotyntsev M. A., Antipov A. E. Bromate electroreduction from acidic solution at spherical microelectrode under steady-state conditions: theory for the redox-mediator autocatalytic (ec") mechanism // Electrochimica Acta. — 2017. — Vol. 258. — P. 544–553. [ DOI ]
Antipov А. Е., Vorotyntsev M. A. Generalized nernst layer model for convective-diffusion transport. numerical solution for bromide ion electroreduction on inactive rotating disk electrode under steady state conditions // Russian Journal of Electrochemistry. — 2017. — Vol. 53, no. 10. — P. 1134–1142. [ DOI ]
Vorotyntsev M. A., Antipov А. Е. Mediator reduction of bromate anion at rotating disk electrode under steady-state conditions for high current densities // Russian Journal of Electrochemistry. — 2017. — Vol. 53, no. 9. — P. 919–931. [ DOI ]
Vorotyntsev M. A., Antipov А. Е., Tolmachev Y. V. 1d model of steady-state discharge process in hydrogen-bromate flow battery // Electrochimica Acta. — 2016. — Vol. 222. — P. 1555–1561. [ DOI ]
Antipov А. Е., Vorotyntsev M. A. Bromate anion electroreduction on inactive rde under steady-state conditions. numerical study of ion transport processes and comproportionation reaction // Russian Journal of Electrochemistry. — 2016. — Vol. 52, no. 10. — P. 925–932. [ DOI ]
Vorotyntsev M. A., Antipov А. Е. Bromate electroreduction via autocatalytic redox mediation: Ec" mechanism. theory for stationary 1d regime. current limitation by proton transport // Electrochimica Acta. — 2016. — Vol. 290. — P. 950–962. [ DOI ]
Electroreduction of bromate anion in acidic solutions at the inactive rotating disc electrode under steady-state conditions: Numerical modeling of the process with bromate anions being in excess compared to protons / M. A. Vorotyntsev, A. E. Antipov, Y. V. Tolmachev et al. // Doklady Physical Chemistry. — 2016. — Vol. 468, no. 1. — P. 141–147. [ DOI ]
Generalization of the nernst layer model to take into account the difference in diffusivity between the components of the system in bromate reduction in steady-state one-dimensional mode: Current limiting by proton transport / А. Е. Antipov, M. A. Vorotyntsev, Y. V. Tolmachev et al. // Doklady Physical Chemistry. — 2016. — Vol. 471, no. 1. — P. 185–189. [ DOI ]
Vorotyntsev M. A., Antipov А. Е. Generalized nernst layer model: application to bromate anion electroreduction. theory for stationary 1d regime for proton transport limitations // ChemElectroChem. — 2016. — Vol. 3, no. 12. — P. 2227–2242. [ DOI ]
Vorotyntsev M. A., Antipov А. Е. Reduction of bromate anion via autocatalytic redox-mediation by br2/br- redox couple. theory for stationary 1d regime. effect of different nernst layer thicknesses for reactants // Journal of Electroanalytical Chemistry. — 2016. — Vol. 779. — P. 146–155. [ DOI ]
Электровосстановление бромат-аниона в кислых растворах на неактивном ВДЭ в стационарных условиях. Численное моделирование процесса в условиях избытка бромат-аниона по сравнению с протонами / М. А. Воротынцев, А. Е. Антипов, Ю. В. Толмачев и др. // Доклады Академии наук. — 2016. — Т. 468, № 1. — С. 37–43. [ DOI ]
Антипов А. Е., Воротынцев М. А. Электровосстановление бромат-аниона на неактивном ВДЭ в стационарных условиях. Численное исследование процессов ионного транспорта и реакции конпропорционирования // Электрохимия. — 2016. — Т. 52, № 10. — С. 1039–1047.
Biased diffusion in tubes of alternating diameter: Numerical study over a wide range of biasing force / Y. A. Makhnovskii, A. M. Berezhkovskii, A. E. Antipov, V. Y. Zitserman // Journal of Chemical Physics. — 2015. — Vol. 143, no. 17. — P. 174102. This paper is devoted to particle transport in a tube formed by alternating wide and narrow sections, in the presence of an external biasing force. The focus is on the effective transport coefficients—mobility and diffusivity, as functions of the biasing force and the geometric parameters of the tube. Dependences of the effective mobility and diffusivity on the tube geometric parameters are known in the limiting cases of no bias and strong bias. The approximations used to obtain these results are inapplicable at intermediate values of the biasing force. To bridge the two limits Brownian dynamics simulations were run to determine the transport coefficients at intermediate values of the force. The simulations were performed for a representative set of tube geometries over a wide range of the biasing force. They revealed that there is a range of the narrow section length, where the force dependence of the mobility has a maximum. In contrast, the diffusivity is a monotonically increasing function of the force. A simple formula is proposed, which reduces to the known dependences of the diffusivity on the tube geometric parameters in both limits of zero and strong bias. At intermediate values of the biasing force, the formula catches the diffusivity dependence on the narrow section length, if the radius of these sections is not too small. [ DOI ]
Зицерман В. Ю., Махновский Ю. А., Антипов А. Е. ДИФФУЗИОННЫЙ ТРАНСПОРТ В ЦИЛИНДРЕ ПЕРЕМЕННОГО СЕЧЕНИЯ // Естественные и математические науки в современном мире: сб. ст. по матер. XXVII междунар. науч.-практ. конф. — Т. 2 из 26. — Сибак Новосибирск, 2015. — С. 184–190.
Biased diffusion in tubes of alternating diameter: Analytical treatment in the case of strong bias / V. Y. Zitserman, A. M. Berezhkovskii, A. E. Antipov, Y. A. Makhnovskii // Journal of Chemical Physics. — 2014. — Vol. 141, no. 21. — P. 214103–1–214103–8. This paper is devoted to the effective transport coefficients of a particle in a tube of alternating diameter. Analytical expressions are derived for the effective mobility and diffusivity under strong bias conditions, i.e., in the limiting case where the external biasing force tends to infinity. The expressions give the transport coefficients as functions of the geometric parameters of the tube and the external force. They show that the effective diffusivity is a linear function of the square of the external force, whereas the effective mobility is independent of the force. The problem of finding effective transport coefficients in a tube of alternating diameter is too complex to be analyzed by conventional methods. Therefore, the expressions are derived in the framework of an intuition-based approach and validated by Brownian dynamics simulations. The obtained results extend a short list of available analytical expressions for the effective transport coefficients. [ DOI ]
Diffusion in a tube consisting of alternating wide and narrow sections / A. E. Antipov, Y. A. Makhnovskii, V. Y. Zitserman, S. M. Aldoshin // Russian Journal of Physical Chemistry B. — 2014. — Vol. 8, no. 5. — P. 752–759. The problem of the diffusion of particles in a tube consisting of identical units, each composed of a wide and narrow section is solved. With an approach based on reducing the problem to a onedimensional, the statistics of times of particle transition between adjacent sections is determined, which is a detailed characteristic of the diffusion process. An expression for the effective diffusion coefficient Def, defining the slowdown of transport due to variations of the tube profile, is derived. It is shown that Def behaves monotonically with increasing length of both the narrow and wide sections. The predictions of analytical formulas are in good agreement with the results of computer simulation performed by the Brownian dynamics method. [ DOI ]
Diffusion in quasi-one-dimensional periodic structures / A. E. Antipov, V. Y. Zitserman, Y. A. Makhnovskii, S. M. Doklady Physical Chemistry Aldoshin // Doklady Physical Chemistry. — 2014. — Vol. 454, no. 2. — P. 32–35. [ DOI ]
High-resolution thermal imaging with a combination of nano-focus x-ray diffraction and ultra-fast chip calorimetry / M. Rosenthal, D. Doblas, J. J. Hernandez et al. // Journal of Synchrotron Radiation. — 2014. — Vol. 21, no. 1. — P. 223–228. [ DOI ]
Nanocomposites and high modulus fibers based on ultrahigh molecular weight polyethylene and silicates: Synthesis, structure, and properties / E. M. Khar’kova, D. I. Mendeleev, V. A. Aulov et al. // Polymer Science, Series A. — 2014. — Vol. 56, no. 1. — P. 72–82. Nanocomposites based on ultrahigh-molecular-weight polyethylene and inorganic fillers—such as organomodified layered aluminosilicates, aerosil, and diatomite—are prepared via polymerization filling. The polymerization of ethylene was conducted in the suspension mode with the use of a conventional Ziegler-Natta catalyst, TiCl4 + Al(i-Bu)3, under mild conditions (a temperature of 30oC and a pressure of 0.1MPa). The structure and properties of the composites are studied via X-ray diffraction analysis and DSC. The polyethylene matrix features a high enthalpy, a high melting temperature (up to 143oC), a crystallinity of 70–80%, a content of the monoclinic phase of 12–15%, and a bulk density of 0.05–0.15 g/cm3; the molecular mass is (1.5–1.6) × 106. High-modulus, high-strength fibers with an elastic modulus of 25–28 GPa and a strength of 0.65–0.70 GPa are prepared via direct solvent-free molding of nascent reactor powders based on ultrahigh-molecular-weight polyethylene filled (7 wt %) with aerosol or montmorillonite modified with vinyltrimethoxysilane. [ DOI ]
ДИФФУЗИЯ В ТРУБКЕ, СОСТОЯЩЕЙ ИЗ ЧЕРЕДУЮЩИХСЯ ШИРОКИХ И УЗКИХ УЧАСТКОВ / А. Е. Антипов, Ю. А. Махновский, В. Ю. Зицерман, С. М. Алдошин // Химическая физика. — 2014. — Т. 33, № 9. — С. 78–86. Рассмотрена задача о диффузии частиц в трубке, состоящей из идентичных фрагментов, каждый из которых включает в себя широкий и узкий участки. С помощью подхода, основанного на редукции задачи к одномерной, найдена статистика времен перехода частицы между соседними фрагментами, которая является детальной характеристикой диффузионного процесса. Получено выражение для эффективного коэффициента диффузии Def, определяющего замедление транспорта благодаря вариации формы трубки. Показано, что Def ведет себя немонотонно с ростом протяженности как узкого, так и широкого участков. Предсказания аналитических расчетов находятся в хорошем согласии с результатами компьютерного моделирования, выполненного методом броуновской динамики. [ DOI ]
Диффузия в квазиодномерных периодических структурах / А. Е. Антипов, В. Ю. Зицерман, Ю. А. Махновский, С. М. Алдошин // Доклады Академии наук. — 2014. — Т. 454, № 6. — С. 676–679.
Нанокомпозиты и высокомодульные волокна на основе сверхвысокомолекулярного полиэтилена и силикатов. Получение, строение, свойства / Е. М. Харькова, Д. И. Менделеев, В. А. Аулов и др. // Высокомолекулярные соединения. Серия А. — 2014. — Т. 56, № 1. — С. 78–89. Методом полимеризационного наполнения получены нанокомпозиты на основе сверхвысокомо? лекулярного полиэтилена и неорганических наполнителей: органомодифицированных слоистых алюмосиликатов, аэросила, диатомита. Полимеризацию этилена осуществляли в суспензионном режиме на традиционном катализаторе Циглера–Натта [TiCl4 + Al(i?Bu)3] в мягких условиях (тем? пература 30oC, давление 0.1 МПа). Структуру и свойства полученных композитов исследовали ме? тодами рентгеноструктурного анализа, дифференциальной сканирующей калориметрии. Для поли? этиленовой матрицы характерны высокие значения энтальпии и температуры плавления (до 143oC), кристалличность 70–80%, содержание моноклинной фазы 12–15%, насыпная плот? ность 0.05–0.15 г/см3. Молекулярная масса составляет 1.5–1.6 млн. Методом прямого безраствор? ного формования насцентных реакторных порошков нанокомпозитов на основе сверхвысокомоле? кулярного полиэтилена, наполненного (7 мас. %) аэросилом либо монтмориллонитом, модифици? рованным винилтриметоксисиланом, получены высокомодульные, высокопрочные волокна с модулем упругости 25–28 ГПа и прочностью 0.65–0.70 ГПа. [ DOI ]
Антипов А. Е., Зицерман В. Ю., Махновский Ю. А. ЭНТРОПИЙНЫЙ МЕХАНИЗМ ФУНКЦИОНИРОВАНИЯ БРОУНОВСКОГО МОТОРА // На стыке наук. Физико-химическая серия. II международная научная Интернет-конференция. — Т. 1. — Сервис виртуальных конференций PAX GRID Казань Казань, 2014. — С. 10–14. [ DOI ]
Antipov A. E., Zitserman V. Y., Makhnovskii Y. A. Asymmetry of the shape of surroundings as a mechanism for generating directed motion // Technical Physics. — 2013. — Vol. 58, no. 11. — P. 1563–1570. [ DOI ]
Effective diffusion coefficient of a brownian particle in a periodically expanded conical tube / A. E. Antipov, A. V. Barzykin, A. M. Berezhkovskii et al. // Physical Review E - Statistical, Nonlinear, and Soft Matter Physics. — 2013. — Vol. 88, no. 5. — P. 054101. [ DOI ]
Антипов А. Е., Махновский Ю. А., Зицерман В. Ю. Асимметрия формы окружения как механизм генерации направленного движения // Журнал технической физики. — 2013. — Т. 83, № 11. — С. 15–23.
Влияние протон-акцепторных добавок на процесс электрополимеризации незамещенного порфина магния / Д. В. Конев, М. А. Воротынцев, Ю. А. Добровольский и др. // Альтернативная энергетика и экология. — 2013. — № 15 (137). — С. 102–109.
НОВЫЙ МЕТОД ПЕРИОДИЧЕСКИХ ДВОЙНЫХ КАТОДНО-АНОДНЫХ ИМПУЛЬСОВ ДЛЯ ЕДИНОВРЕМЕННОГО ОСАЖДЕНИЯ КОМПОЗИТНЫХ ПЛЕНОК НЕОРГАНИЧЕСКИЙ КОМПОНЕНТ -ЭЛЕКТРОАКТИВНЫЙ ПОЛИМЕР ИЗ СМЕШАННОГО РАСТВОРА ИХ ПРЕКУРСОРОВ / Е. В. Золотухина, М. А. Воротынцев, Д. В. Конев и др. // Альтернативная энергетика и экология. — 2013. — № 13 (135). — С. 49–58. Предложен новый электрохимический метод одностадийного осаждения композитных пленок на поверхности электрода. Процедура включает в себя периодическую серию импульсов потенциала или тока переменных полярностей, налагаемых на электрод в контакте со смешанным раствором двух прекурсоров, один из которых способен формировать твердую фазу при электроокислении, а другой - при электровосстановлении. В качестве иллюстрации этот метод был применен для выращивания композитных пленок берлинская лазурь-полипиррол.
Zitserman V. Y., Makhnovskii Y. A., Antipov A. E. Directed transport of a brownian particle in a periodically tapered tube // Journal of Experimental and Theoretical Physics. — 2012. — Vol. 142, no. 3. — P. 535–549.
Махновский Ю. А., Зицерман В. Ю., Антипов А. Е. НАПРАВЛЕННЫЙ ТРАНСПОРТ БРОУНОВСКОЙ ЧАСТИЦЫ В ПЕРИОДИЧЕСКИ СУЖАЮЩЕЙСЯ ТРУБКЕ // Журнал экспериментальной и теоретической физики. — 2012. — Т. 142, № 9. — С. 603–620. Рассмотрена задача о движении броуновской частицы в периодически сужающейся трубке, обусловленном периодически меняющейся со временем продольной силой, в среднем равной нулю. Показано, что под действием этой силы частица дрейфует в направлении, об¬ратном приложенной к ней постоянной силе нагрузки. При большой амплитуде движущей силы, когда обсуждаемый эффект максимален, получены аналитические решения для скорости дрейфа, силы остановки (величины нагрузки, обнуляющей эффект) и эффективности преобразования энергии вносимых возмущений в направленное движение. В области своей применимости, простирающейся от нуля до асимптотически больших частот переключения силы (пропорциональных амплитуде движущей силы), эти решения находятся в прекрасном согласии с результатами компьютерного моделирования, выполненного методом броуновской динамики.
Communication: Drift velocity of brownian particle in a periodically tapered tube induced by a time-periodic force with zero mean: Dependence on the force period / V. Y. Zitserman, A. M. Berezhkovskii, A. E. Antipov, Y. A. Mahnovskii // Journal of Chemical Physics. — 2011. — Vol. 135, no. 12. — P. 121102. [ DOI ]
Highly oriented fibers of biodegradable polyhydroxyalkanoates / E. M. Antipov, A. V. Rebrov, Y. P. Nekrasov et al. // Экология и промышленность России. — 2010. — Vol. 5. — P. 2–8. Polyhydroxyalkanoates are the polymers, which active studying is connected, first of all, to the problem of producing strong biodegradable fibers and skins, capable to degrade in the environment up to non-toxic waste products that is dictated by the problems of ecology when recycling packing products and creation of novel medical materials. For obtaining samples in oriented condition (fibers or tubular products), there are developed at the Institute of Petrochemical Synthesis of the Russian Academy of Science the novel original approaches giving possibility to lower the temperature of forming down to safe one for thermally destructing polymer and thus to leave reserve of time for orienting extraction of macromole-cules prior to the beginning of intensive crystallization. For the first time, the samples possessing meso-phase structure of columnar type and unusual "hard-elastic" properties, or, on the contrary, high-module fibers are obtained.
Высокоориентированные волокна биодеградируемых полигидроксиалканоатов / Е. М. Антипов, А. В. Ребров, Ю. П. Некрасов и др. // Экология и промышленность России. — 2010. — № 5. — С. 30–36.