chemicallytechFine Chemical TechnologiesТонкие химические технологии2410-65932686-7575MIREA – Russian Technological University (RTU MIREA).10.32362/2410-6593-2026-21-1-109-119PBLSBFchemicallytech-2355Research ArticleCHEMISTRY AND TECHNOLOGY OF INORGANIC MATERIALSХИМИЯ И ТЕХНОЛОГИЯ НЕОРГАНИЧЕСКИХ МАТЕРИАЛОВSurface and bulk thermodynamic factors of Ba0.5Sr0.5(Co0.8Fe0.2)1−xMexO3−δ (Me = Ta, W) oxidesОбъемный и поверхностный термодинамические факторы оксидов Ba0.5Sr0.5(Co0.8Fe0.2)1−xMexO3−δ (Me = Ta, W)https://orcid.org/0000-0003-3863-0043АхмадеевА. Р.AkhmadeevAlbert R.

Ахмадеев Альберт Рустемович, аспирант; старший научный сотрудник лаборатории Электрохимических устройств для водородной энергетики,

142432, Московская обл., г. Черноголовка, Северный пр., д. 1; 

111524, Москва, Электродная ул., д. 2, стр. 1.

Scopus Author ID: 58243031000.

ResearcherID: HPF-3683-2023.

Albert R. Akhmadeev, Postgraduate Student; Senior Researcher, Laboratory of the Electrochemical Devices for Hydrogen Energy,

1, Severnyi pr., Chernogolovka, Moscow oblast, 142432; 

2-1, Electrodnaya ul., Moscow, 111524. 

ResearcherID: HPF-3683-2023.

Scopus Author ID: 58243031000.

albertakhmadeev1@gmail.comhttps://orcid.org/0000-0002-1897-4618ЕреминВ. А.EreminVadim А.

Еремин Вадим Анатольевич, к.х.н., начальник лаборатории Электрохимических устройств для водородной энергетики,

111524, Москва, Электродная ул., д. 2, стр. 1).

Scopus Author ID: 7103377859.

ResearcherID: L-6709-2017.

Vadim А. Eremin, Cand. Sci. (Chem.), Head of the Laboratory of the Electrochemical Devices for Hydrogen Energy,

2-1, Electrodnaya ul., Moscow, 111524,

Scopus Author ID: 7103377859.

ResearcherID: L-6709-2017.

v-eremin@list.ruhttps://orcid.org/0000-0002-2254-0193АнаньевМ. В.AnanyevMaxim V.

Ананьев Максим Васильевич, д.х.н., начальник Управления технологий и Материалов Четвертого Энергетического Перехода; профессор кафедры информационных компьютерных технологий

111524, Москва, Электродная ул., д. 2, стр. 1);

125047, Москва, Миусская пл., д. 9.

Scopus Author ID: 15061114600.

ResearcherID: F-5104-2014. 

Maxim V. Ananyev, Dr. Sci. (Chem.), Head of the Department of the Technology and Materials of the Fourth Energy; Professor, Department of Information Computer Technologies, 

2-1, Electrodnaya ul., Moscow, 111524;

9, Miusskaya pl., Moscow, 125047.

Scopus Author ID: 15061114600, ResearcherID: F-5104-2014.

m.ananyev@mail.ruФедеральный исследовательский центр проблем химической физики и медицинской химии Российской академии наук (ФИЦ ПХФ и МХ РАН); Государственный научно-исследовательский и проектный институт редкометаллической промышленности имени Н.П. Сажина (АО «Гиредмет»)РоссияFederal Research Center of Problems of Chemical Physics and Medical Chemistry, Russian Academy of Sciences; Federal State Research and Design Institute of Rare Metal Industry (Giredmet)Russian FederationГосударственный научно-исследовательский и проектный институт редкометаллической промышленности имени Н.П. Сажина (АО «Гиредмет»)РоссияFederal State Research and Design Institute of Rare Metal Industry (Giredmet)Russian FederationГосударственный научно-исследовательский и проектный институт редкометаллической промышленности имени Н.П. Сажина (АО «Гиредмет»); Российский химико-технологический университет им. Д.И. МенделееваРоссияFederal State Research and Design Institute of Rare Metal Industry (Giredmet); Mendeleev University of Chemical Technology of RussiaRussian Federation202605032026211109119Copyright © Akhmadeev A.R., Eremin V.А., Ananyev M.V., 20262026Ахмадеев А.Р., Еремин В.А., Ананьев М.В.Akhmadeev A.R., Eremin V.А., Ananyev M.V.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://www.finechem-mirea.ru/jour/article/view/2355Objectives

Objectives. In this work, we consider the relationship between the tracer (k*) and chemical (kδ) oxygen exchange coefficients for Ba0.5Sr0.5(Co0.8Fe0.2)1−xMexO3−δ (Me = Ta, W) oxides. The aim is to analyze the experimental dependencies of the chemical (kδ) and tracer (k*) coefficients of oxygen exchange, evaluate the surface thermodynamic factor w0|x=±L , and compare its value with the bulk thermodynamic factor w0|x=0 determined from the dependence of oxygen content in oxides on the temperature and partial pressure of oxygen. Possible reasons for the discrepancy between these two thermodynamic factors are discussed.

Methods

Methods. The oxygen exchange kinetics between the gas phase and the surface of oxide materials under nonequilibrium conditions was studied using the method of oxygen pressure relaxation. The surface thermodynamic factor was calculated based on data obtained under both equilibrium and nonequilibrium conditions.

Results

Results. Comparison of the tracer (k*) and chemical (kδ) oxygen exchange coefficients allowed the w0|x=±L surface thermodynamic factor to be estimated by the kδ = k*w0|x=±L equation.

Conclusions

Conclusions. The surface thermodynamic factor was found to differ from the bulk thermodynamic factor of the oxide material, w0 = [1∂ln(pO2 )] / [2 ∂ln (3−δ)], which can be calculated from the dependence of oxygen content in oxides on the temperature and partial pressure of oxygen. This difference can be explained by the difference in the defect structure of the surface layers of oxide materials.

Цели

Цели. Работа посвящена анализу взаимосвязи изотопного k* и химического kδ коэффициентов обмена кислородом для оксидов Ba0.5Sr0.5(Co0.8Fe0.2)1−xMexO3−δ (Me = Ta, W). Целью работы является анализ экспериментальных зависимостей химического и изотопного коэффициентов обмена кислорода, оценка поверхностного термодинамического фактора w0|x=±L и сравнение его с объемным термодинамическим фактором w0|x=0, определенным из зависимости содержания кислорода в оксидах от температуры и парциального давления кислорода. В статье обсуждаются возможные причины несовпадения двух термодинамических факторов.

Методы

Методы. Изучение кинетики обмена кислородом газовой фазы с поверхностью оксидных материалов в неравновесных условиях проведено методом релаксации давления кислорода. Расчет поверхностного термодинамического фактора проведен на основе данных, полученных в равновесных и неравновесных условиях.

Результаты

Результаты. Сравнение изотопного k* и химического kδ коэффициентов обмена кислорода позволило оценить поверхностный термодинамический фактор w0|x=±L через уравнение kδ = k*w0|x=±L.

Выводы

Выводы. Было обнаружено, что поверхностный термодинамический фактор отличается от термодинамического фактора, относящегося к объему оксидного материала w0 = [1∂ln(pO2)] / [2 ∂ln (3−δ)], который может быть рассчитан из зависимостей содержания кислорода в оксидах от температуры и парциального давления кислорода. Такое различие было объяснено различием в дефектной структуре поверхностных слоев оксидных материалов.

поверхностный обмен кислородадиффузия кислородаBSCFрелаксация давления кислородамембрана со смешанной ионно-электронной проводимостьютермодинамический факторsurface oxygen exchangeoxygen diffusionBSCFoxygen pressure relaxationmixed ionic-electronic conduction membranethermodynamic factorВ работе использовались возможности центров коллективного доступа «Состав соединений» и Уникальной научной установки «Изотопный обмен» Института высокотемпературной электрохимии Уральского отделения Российской академии наук. Работа частично выполнена в рамках программы развития Российского химико-технологического университета имени Д.И. Менделеева «Приоритет-2030». Авторы также благодарны проекту ЕОТП-ВЭ-665.This work utilized the capabilities of the “Composition of Compounds” Shared Access Centers and the Unique “Isotope Exchange” Research Facility at the Institute of High-Temperature Electrochemistry, Ural Branch, Russian Academy of Sciences. 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The authors declare that there are no conflicts of interest present.