Объемный и поверхностный термодинамические факторы оксидов Ba_0.5Sr_0.5(Co_0.8Fe_0.2)_1−xMe_xO_3−δ (Me = Ta, W)

Цели. Работа посвящена анализу взаимосвязи изотопного k* и химического k^δ коэффициентов обмена кислородом для оксидов Ba_0.5Sr_0.5(Co_0.8Fe_0.2)_1−xMe_xO_3−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. 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. Сравнение изотопного k* и химического k^δ коэффициентов обмена кислорода позволило оценить поверхностный термодинамический фактор w₀|_x=±L через уравнение k^δ = k^*w₀|_x=±L.

Выводы. Было обнаружено, что поверхностный термодинамический фактор отличается от термодинамического фактора, относящегося к объему оксидного материала w₀ = [1^∂ln(p_O2)] / [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.

1. Geffroy P.M., Fouletier J., Richet N., Chartier T. Rational selection of MIEC materials in energy production processes. Chem. Eng. Sci. 2013;87:408–433. https://doi.org/10.1016/j.ces.2012.10.027

2. Sunarso J., Baumann S., Serra J.M., Meulenberg W.A., Liu S., Lin Y.S., Diniz da Costa J.C. Mixed ionic-electronic conducting (MIEC) ceramic-based membranes for oxygen separation. J. Membrane Sci. 2008;320(1-2):13–41. https://doi.org/10.1016/j.memsci.2008.03.074

3. Sahini M.G., Mwankemwa B.S., Kanas N. Bax Sr1−x Coy Fe1−y O3−δ (BSCF) mixed ionic-electronic conducting (MIEC) materials for oxygen separation membrane and SOFC applications: Insights into processing, stability, and functional properties. Ceramics Int. 2022;48(3):2948–2964. https://doi.org/10.1016/j.ceramint.2021.10.189

4. Bouwmeester H.J.M., Burggraaf A.J. Chapter 10. Dense ceramic membranes for oxygen separation. In: Membrane Science and Technology. V. 4. Elsevier; 1996. P. 435–528. https://doi.org/10.1016/S0927-5193(96)80013-1

5. Markov A.A., Merkulov O.V., Suntsov A.Yu. Development of Membrane Reactor Coupling Hydrogen and Syngas Production. Membranes. 2023;13(7):626. https://doi.org/10.3390/membranes13070626

6. Sunarso J., Hashim S.S., Zhu N., Zhou W. Perovskite oxides applications in high temperature oxygen separation, solid oxide fuel cell and membrane reactor: A review. Progress in Energy and Combustion Science. 2017;61:57–77. https://doi.org/10.1016/j.pecs.2017.03.003

7. Suntsov A.Yu., Marshenya S.N., Markov A.A., Kozhevnikov V.L. Performance of the layered cobaltites in membrane mediated oxygen separation from air and methane partial oxidation. Mater. Lett. 2021;295:129818. https://doi.org/10.1016/j.matlet.2021.129818

8. Bouwmeester H.J.M., Kruidhof H., Burggraaf A.J. Importance of the surface exchange kinetics as rate limiting step in oxygen permeation through mixed-conducting oxides. Solid State Ionics. 1994;72(Part 2):185–194. https://doi.org/10.1016/0167-2738(94)90145-7

9. Lin Y.-S., Wang W., Han J. Oxygen permeation through thin mixed-conducting solid oxide membranes. AIChE J. 1994;40:786–798. https://doi.org/10.1002/aic.690400506

10. Bouwmeester H.J.M., Krmdhof H., Burggraaf A.J., Gelhngs P.J. Oxygen semipermeability of erbia-stabilized bismuth oxide. Solid State Ionics. 1992;53-56(Part 1): 460–468. https://doi.org/10.1016/0167-2738(92)90416-M

11. Dou S., Masson C.R., Pacey P.D. Mechanism of Oxygen Permeation Through Lime‐Stabilized Zirconia. J. Electrochem. Soc. 1985;132(8):1843–1849. https://doi.org/10.1149/1.2114228

12. Vanhassel B., Kawada T., Sakai N., Yokokawa H., Dokiya M., Bouwmeester H. Oxygen permeation modelling of perovskites. Solid State Ionics. 1993;66(3-4):295–305. https://doi.org/10.1016/0167-2738(93)90419-4

13. Cao G.Z. Electrical conductivity and oxygen semipermeability of terbia and yttria stabilized zirconia. J. Appl. Electrochem. 1994;24:1222–1227. https://doi.org/10.1007/BF00249885

14. Wagner C. Beitrag zur Theorie des Anlaufvorgangs. Z. Physikal. Chem. 1933;21B(1):25–41. https://doi.org/10.1515/zpch-1933-2105

15. Wagner C. Beitrag zur Theorie des Anlaufvorganges. II. Z. Physikal. Chem. 1936;32B(1):447–462. https://doi.org/10.1515/zpch-1936-3239

16. Wagner C. Equations for transport in solid oxides and sulfides of transition metals. Progress in Solid State Chemistry. 1975;10(Part 1): 3–16. https://doi.org/10.1016/0079-6786(75)90002-3

17. Akhmadeev A.R., Eremin V.A., Ananyev M.V., Voloshin B.V., Popov M.P., Ivanov I.L., Fetisov A.V. Oxygen stoichiometry and isotope exchange of oxides Ba0.5Sr0.5Co0.8Fe0.2O3−δ doped with Ta, Nb, Mo or W. Appl. Surface Sci. 2023;629:157312. https://doi.org/10.1016/j.apsusc.2023.157312

18. Eremin V.A., Ananyev M.V., Bouwmeester H.J.M., Kurumchin E.K., Yoo C.Y. Oxygen surface exchange kinetics of Ba0.5Sr0.5Co0.8Fe0.2O3−δ. Phys. Chem. Chem. Phys. 2020;22(18):10158–10169. https://doi.org/10.1039/c9cp06650k

19. Ananyev M.V., Eremin V.A., Tsvetkov D.S., Porotnikova N.M., Farlenkov A.S., Zuev A.Y., Fetisov A.V., Kurumchin E.K. Oxygen isotope exchange and diffusion in LnBaCo2O6−δ (Ln = Pr, Sm, Gd) with double perovskite structure. Solid State Ionics. 2017;304: 96–106. https://doi.org/10.1016/j.ssi.2017.03.022

20. Berenov A.V., Atkinson A., Kilner J.A., Bucher E., Sitte W. Oxygen tracer diffusion and surface exchange kinetics in La0.6Sr0.4CoO3−δ. Solid State Ionics. 2010;181(17-18): 819–826. https://doi.org/10.1016/j.ssi.2010.04.031

21. Benson S.J., Chater R., Kilner J.A. Oxygen diffusion and surface exchange in the mixed conducting perovskite La0.6Sr0.4Fe0.8Co0.2O3−δ. In: Ramanarayanan T.A. (Ed.). Ionic and Mixed Conducting Ceramics: Proceedings of the Third International Symposium. Electrochemical Society; 1998. V. 97–24. P. 596–609. https://books.google.ru/books?id=30NC4dcoghAC&hl=ru&source=gbs_navlinks_s

22. Wang L., Merkle R., Maier J., Acartürk T., Starke U. Oxygen tracer diffusion in dense Ba0.5Sr0.5Co0.8Fe0.2O3−δ films. Appl. Phys. Lett. 2009;94:071908. https://doi.org/10.1063/1.3085969

23. Fullarton I.C., Jacobs J.-P., Van Benthem H.E., Kilner J.A., Brongersma H.H., Scanlon P.J., Steele B.C.H. Study of oxygen ion transport in acceptor doped samarium cobalt oxide. Ionics. 1995;1:51–58. https://doi.org/10.1007/BF02426008

24. De Souza R.A., Kilner J.A. Oxygen transport in La1−x Srx Mn1−y Coy O3±δ perovskites: Part I. Oxygen tracer diffusion. Solid State Ionics. 1998;106(3-4):175–187. https://doi.org/10.1016/s0167-2738(97)00499-2

25. Kriegel R., Kircheisen R., Töpfer J. Oxygen stoichiometry and expansion behavior of Ba0.5Sr0.5Co0.8Fe0.2O3−δ. Solid State Ionics. 2010;181(1-2):64–70. https://doi.org/10.1016/j.ssi.2009.11.012

26. Bucher E., Egger A., Ried P., Sitte W., Holtappels P. Oxygen nonstoichiometry and exchange kinetics of Ba0.5Sr0.5Co0.8Fe0.2O3−δ. Solid State Ionics. 2008;179(21-26): 1032–1035. https://doi.org/10.1016/j.ssi.2008.01.089

27. McIntosh S., Vente J.F., Haije W.G., Blank D.H.A., Bouwmeester H.J.M. Structure and oxygen stoichiometry of SrCo0.8Fe0.2O3−δ and Ba0.5Sr0.5Co0.8Fe0.2O3−δ. Solid State Ionics. 2006;177(19-25):1737–1742. https://doi.org/10.1016/j.ssi.2006.03.041

28. Jun A., Yoo S., Gwon O.H., Shin J., Kim G. Thermodynamic and electrical properties of Ba0.5Sr0.5Co0.8Fe0.2O3−δ and La0.6Sr0.4Co0.2Fe0.8O3−δ for intermediate-temperature solid oxide fuel cells. Electrochimica Acta. 2013;89:372–376. https://doi.org/10.1016/j.electacta.2012.11.002

29. Mueller D.N., De Souza R.A., Yoo H.I., Martin M. Phase stability and oxygen nonstoichiometry of highly oxygen-deficient perovskite-type oxides: A case study of (Ba,Sr)(Co,Fe)O3−δ. Chem. Mater. 2012;24(2):269–274. https://doi.org/10.1021/cm2033004

30. Wang L., Merkle R., Mastrikov Y.A., Kotomin E.A., Maier J. Oxygen exchange kinetics on solid oxide fuel cell cathode materials-general trends and their mechanistic interpretation. J. Mater. Res. 2012;27(15):2000–2008. https://doi.org/10.1557/jmr.2012.186

31. Bouwmeester H.J.M., Song C., Zhu J., Yi J., Van Sint Annaland M., Boukamp B.A. A novel pulse isotopic exchange technique for rapid determination of the oxygen surface exchange rate of oxide ion conductors. Phys. Chem. Chem. Phys. 2009;11(42): 9640–9643. https://doi.org/10.1039/b912712g

32. Berenov A., Atkinson A., Kilner J., Ananyev M., Eremin V., Porotnikova N., Farlenkov A., Kurumchin E., Bouwmeester H.J.M., Bucher E., Sitte W. Oxygen tracer diffusion and surface exchange kinetics in Ba0.5Sr0.5Co0.8Fe0.2O3−δ. Solid State Ionics. 20914;268(Part A): 102–109. https://doi.org/10.1016/j.ssi.2014.09.031

33. Maier J. On the correlation of macroscopic and microscopic rate constants in solid state chemistry. Solid State Ionics. 1998; 112(3-4):197–228. https://doi.org/10.1016/S0167-2738(98)00152-0

34. Ananyev M.V., Porotnikova N.M., Kurumchin E.K. Influence of strontium content on the oxygen surface exchange kinetics and oxygen diffusion in La1–x Srx CoO3–δ oxides. Solid State Ionics. 2019;341:115052. https://doi.org/10.1016/j.ssi.2019.115052

35. Ananyev M.V., Tropin E.S., Eremin V.A., Farlenkov A.S., Smirnov A.S., Kolchugin A.A., Porotnikova N.M., Khodimchuk A.V., Berenov A.V., Kurumchin E.Kh. Oxygen isotope exchange in La2NiO4±δ. Phys. Chem. Chem. Phys. 2016;18(13):9102–9111. https://doi.org/10.1039/C5CP05984D

36. Porotnikova N.M., Eremin V.A., Farlenkov A.S., Kurumchin E.K., Sherstobitova E.A., Kochubey D.I., Ananyev M.V. Effect of AO Segregation on Catalytical Activity of La0.7A0.3MnO3±δ (A = Ca, Sr, Ba) Regarding Oxygen Reduction Reaction. Catal. Lett. 2018;148: 2839–2847. https://doi.org/10.1007/s10562-018-2456-7

37. Popov M.P., Starkov I.A., Bychkov S.F., Nemudry A.P. Improvement of Ba0.5Sr0.5Co0.8Fe0.2O3−δ functional properties by partial substitution of cobalt with tungsten. J. Membrane Sci. 2014;469:88–94. https://doi.org/10.1016/j.memsci.2014.06.022

38. Akhmadeev A.R., Eremin V.A., Ananyev M.V. Kinetics of oxygen exchange with oxides Ba0.5Sr0.5(Co0.8Fe0.2) 1−x Mex O3−ẟ (Me = Ta, W) in non-equilibrium conditions. J. Solid State Electrochem. 2024;29:4973–4983. https://doi.org/10.1007/s10008-024-06034-x

39. Fleig J., Merkle R., Maier J. The p(O2) dependence of oxygen surface coverage and exchange current density of mixed conducting oxide electrodes: model considerations. Phys. Chem. Chem. Phys. 2007;9(21):2713–2723. https://doi.org/10.1039/b618765j

40. Maier J. Interaction of oxygen with oxides: How to interpret measured effective rate constants? Solid State Ionics. 2000; 135(1-4):575–588. https://doi.org/10.1016/S0167-2738(00)00438-0

41. Adler S., Chen X., Wilson J. Mechanisms and rate laws for oxygen exchange on mixed-conducting oxide surfaces. J. Catalysis. 2007;245(1):91–109. https://doi.org/10.1016/j.jcat.2006.09.019

42. Adler S.B. Factors governing oxygen reduction in solid oxide fuel cell cathodes. Chem. Rev. 2004;104(10):4791–4843. https://doi.org/10.1021/cr020724o

43. Porotnikova N., Farlenkov A., Naumov S., Vlasov M., Khodimchuk A., Fetisov A., Ananyev M. Effect of grain boundaries in La0.84Sr0.16CoO3−δ on oxygen diffusivity and surface exchange kinetics. Phys. Chem. Chem. Phys. 2021;23(19):11272–11286. https://doi.org/10.1039/d1cp01099a

44. Ten Elshof J.E., Lankhorst M.H.R., Bouwmeester H.J.M. Oxygen Exchange and Diffusion Coefficients of Strontium‐ Doped Lanthanum Ferrites by Electrical Conductivity Relaxation. J. Electrochem. Soc. 1997;144(3):1060–1067. https://doi.org/10.1149/1.1837531

45. Lane J.A., Benson S.J., Waller D., Kilner J.A. Oxygen transport in La0.6Sr0.4Co0.2Fe0.8O3−δ. Solid State Ionics. 1999;121(1-4): 201–208. https://doi.org/10.1016/S0167-2738(99)00014-4

46. Geffroy P.M., Blond E., Richet N., Chartier T. Understanding and identifying the oxygen transport mechanisms through a mixed-conductor membrane. Chem. Eng. Sci. 2017;162: 245–261. https://doi.org/10.1016/j.ces.2017.01.006

47. Egger A., Bucher E., Yang M., Sitte W. Comparison of oxygen exchange kinetics of the IT-SOFC cathode materials La0.5Sr0.5CoO3−δ and La0.6Sr0.4CoO3−δ. Solid State Ionics. 2012;225:55–60. https://doi.org/10.1016/j.ssi.2012.02.050

48. Ten Elshof J.E., Lankhorst M.H.R., Bouwmeester H.J.M. Chemical diffusion and oxygen exchange of La0.6Sr0.4Co0.6Fe0.4O3−δ. Solid State Ionics. 1997;99(1-2):15–22. https://doi.org/10.1016/S0167-2738(97)00263-4

49. Katsuki M. High temperature properties of La0.6Sr0.4Co0.8Fe0.2O3−δ oxygen nonstoichiometry and chemical diffusion constant. Solid State Ionics. 2003;156(3-4): 453–461. https://doi.org/10.1016/S0167-2738(02)00733-6

50. Gao Z., Mogni L.V., Miller E.C., Railsback J.G., Barnett S.A. A perspective on low-temperature solid oxide fuel cells. Energy Environ. Sci. 2016;9(5):1602–1644. https://doi.org/10.1039/C5EE03858H