zldmЗаводская лаборатория. Диагностика материаловIndustrial laboratory. Diagnostics of materials1028-68612588-0187ООО «Издательство «ТЕСТ-ЗЛ»10.26896/1028-6861-2025-91-5-38-44zldm-2493Research ArticleИССЛЕДОВАНИЕ СТРУКТУРЫ И СВОЙСТВSTRUCTURE AND PROPERTIES INVESTIGATIONИсследование свойств сложного оксида Bi2Co1/3Cu1/3Ni1/3Nb2O9+Δ со структурой пирохлораResearch of the properties of a complex oxide Bi2Co1/3Cu1/3Ni1/3Nb2O9+Δ with a pyrochlore structureПетраковА. П.PetrakovA. P.

Анатолий Павлович Петраков

167001, г. Сыктывкар, Октябрьский пр-т, д. 55

Anatoly P. Petrakov

55, Oktyabrsky prosp., Syktyvkar, 167001

petrakov@syktsu.ruБаданинаК. А.BadaninaK. A.

Ксения Алексеевна Баданина

167001, г. Сыктывкар, Октябрьский пр-т, д. 55

Ksenia A. Badanina

55, Oktyabrsky prosp., Syktyvkar, 167001

petrakov@syktsu.ruСелютинА. А.SelyutinA. A.

Артем Александрович Селютин

198504, г. Санкт-Петербург, Университетский пр-т, д. 26

Artyom A. Selyutin

26, Universitetsky prosp., St. Petersburg, 198504

КоролеваА. В.KorolevaA. V.

Александра Владимировна Королева

198504, г. Санкт-Петербург, Университетский пр-т, д. 26

Alexandra V. Koroleva

26, Universitetsky prosp., St. Petersburg, 198504

НекипеловС. В.NekipelovS. V.

Сергей Вячеславович Некипелов

167982, г. Сыктывкар, ул. Оплеснина, д. 4

Sergey V. Nekipelov

4, ul. Oplesnina, Syktyvkar, 167982

МакеевБ. А.MakeevB. A.

Борис Александрович Макеев

167000, г. Сыктывкар, ул. Первомайская, д. 54

Boris A. Makeev

54, ul. Pervomaiskaya, Syktyvkar, 167000

ЖукН. А.ZhukN. A.

Надежда Алексеевна Жук

167001, г. Сыктывкар, Октябрьский пр-т, д. 55

Nadezhda A. Zhuk

55, Oktyabrsky prosp., Syktyvkar, 167001

Сыктывкарский государственный университет им. Питирима СорокинаРоссияPitirim Sorokin Syktyvkar State UniversityRussian FederationСанкт-Петербургский государственный университетРоссияSt. Petersburg State UniversityRussian FederationИнститут физики и математики Коми НЦ УрО РАНРоссияInstitute of Physics and Mathematics of the Komi Science Center UB RASRussian FederationИнститут геологии им. Н. П. Юшкина Коми НЦ УрО РАНРоссияN. P. Yushkin Institute of Geology of the Komi Science Center UB RASRussian Federation2025270520259153844Copyright © Петраков А.П., Баданина К.А., Селютин А.А., Королева А.В., Некипелов С.В., Макеев Б.А., Жук Н.А., 20252025Петраков А.П., Баданина К.А., Селютин А.А., Королева А.В., Некипелов С.В., Макеев Б.А., Жук Н.А.Petrakov A.P., Badanina K.A., Selyutin A.A., Koroleva A.V., Nekipelov S.V., Makeev B.A., Zhuk N.A.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://www.zldm.ru/jour/article/view/2493

Висмутсодержащие монодопированные пирохлоры обладают перспективными фотокаталитическими и диэлектрическими свойствами. В работе представлены результаты исследования свойств мультиэлементного пирохлора, содержащего переходные 3d-элементы в эквимолярных количествах. Смешанный оксидный пирохлор состава Bi2Co1/3Cu1/3Ni1/3Nb2O9+Δ (пр. гр. Fd-3m, a = 10,5378 ± 6 Å) синтезировали методом твердофазной реакции. Химическое состояние катионов переходных элементов в оксидном пирохлоре оценивали методом рентгеновской фотоэлектронной спектроскопии (XPS). Параметры XPS-спектров Bi5d, Nb3d, Co2p, Ni2p, Cu2p для смешанного пирохлора сопоставляли с параметрами оксидов переходных элементов. На основании анализа относительной интенсивности пиков в спектре Cu2p определяли содержание катионов Cu (I, II). Установлено, что для сложного пирохлора наблюдается характерный сдвиг Bi4f- и Nb3d-спектров в область меньших энергий на величины 0,25 и 0,65 эВ соответственно. Ширина запрещенной зоны пирохлора для прямого разрешенного наиболее интенсивного электронного перехода составляет 1,1 эВ. Полученные результаты могут быть использованы для совершенствования технологии изготовления многослойных керамических конденсаторов и СВЧ диэлектрических материалов.

Bismuth-containing monodoped pyrochlores have promising photocatalytic and dielectric properties. The paper presents the results of studying the properties of multielement pyrochlore containing transition 3d-elements in equivalent amounts. Mixed oxide pyrochlore of the composition Bi2Co1/3Cu1/3Ni1/3Nb2O9+Δ (sp. gr. Fd-3m, a = 10.5378 ± 6 Å) was synthesized by the solid-phase reaction method. The chemical state of transition element cations in the oxide pyrochlore was estimated by X-ray photoelectron spectroscopy (XPS). The parameters of the Bi5d, Nb3d, Co2p, Ni2p, Cu2p XPS spectra for the mixed pyrochlore were compared with the parameters of transition element oxides. The content of Cu (I, II) cations was determined based on the analysis of the relative intensity of peaks in the Cu2p spectrum. It has been established that for complex pyrochlore a characteristic shift of Bi4f- and Nb3d-spectra to the region of lower energies by 0.25 and 0.65 eV, respectively, is observed. The width of the forbidden band of pyrochlore for the direct allowed most intense electronic transition is 1.1 eV. The obtained results can be used to improve the technology of manufacturing multilayer ceramic capacitors and microwave dielectric materials.

твердофазная реакцияоксидный пирохлорспектрыэлектронный переходзапрещенная зонаsolid-phase reactionpyrochlore oxidespectraelectronic transitionband gapReferencesDu H., Yao X. Structural trends and dielectric properties of Bi-based pyrochlores / Journal of Materials Science: Materials in Electronics. 2004. Vol. 15. P. 613 – 616. DOI: 10.1023/b:jmse.0000036041.84889.b2Du H., Yao X. Structural trends and dielectric properties of Bi-based pyrochlores / Journal of Materials Science: Materials in Electronics. 2004. Vol. 15. P. 613 – 616. DOI: 10.1023/b:jmse.0000036041.84889.b2Giampaoli G., Siritanon T., Day B., et al. Temperature independent low loss dielectrics based on quaternary pyrochlore oxides / Progress in Solid State Chemistry. 2018. Vol. 50. P. 16 – 23. DOI: 10.1016/j.progsolidstchem.2018.06.001Giampaoli G., Siritanon T., Day B., et al. Temperature independent low loss dielectrics based on quaternary pyrochlore oxides / Progress in Solid State Chemistry. 2018. Vol. 50. P. 16 – 23. DOI: 10.1016/j.progsolidstchem.2018.06.001Barkovskiy N. V. Methods for identification of Bi (V) and unusual oxygen valence states in BaBiO3 and superconducting oxides of K – Ba – Bi – O system / Industr. Lab. Mater. Diagn. 2019. Vol. 85. No. 8. P. 16 – 28 [in Russian]. DOI: 10.26896/1028-6861-2019-85-8-16-28Barkovskiy N. V. Methods for identification of Bi (V) and unusual oxygen valence states in BaBiO3 and superconducting oxides of K – Ba – Bi – O system / Industr. Lab. Mater. Diagn. 2019. Vol. 85. No. 8. P. 16 – 28 [in Russian]. DOI: 10.26896/1028-6861-2019-85-8-16-28Subramanian M., Aravamudan G., Subba Rao G. Oxide pyrochlores: a review / Progress in Solid State Chemistry. 1983. Vol. 15. P. 55 – 143. DOI: 10.1016/0079-6786(83)90001-8Subramanian M., Aravamudan G., Subba Rao G. Oxide pyrochlores: a review / Progress in Solid State Chemistry. 1983. Vol. 15. P. 55 – 143. DOI: 10.1016/0079-6786(83)90001-8Kamba S., Porokhonsky V., Pashkin A., et al. Anomalous broad dielectric relaxation in Bi1.5Zn1.0Nb1.5O7 pyrochlore / Physical Review B. 2002. Vol. 66. No. 5. Art. 054106. DOI: 10.1103/physrevb.66.054106Kamba S., Porokhonsky V., Pashkin A., et al. Anomalous broad dielectric relaxation in Bi1.5Zn1.0Nb1.5O7 pyrochlore / Physical Review B. 2002. Vol. 66. No. 5. Art. 054106. DOI: 10.1103/physrevb.66.054106Valant M. Dielectric relaxations in Bi2O3 – Nb2O5 – NiO cubic pyrochlores / Journal of the American Ceramic Society. 2009. Vol. 92. P. 955 – 958. DOI: 10.1111/j.1551-2916.2009.02984.xValant M. Dielectric relaxations in Bi2O3 – Nb2O5 – NiO cubic pyrochlores / Journal of the American Ceramic Society. 2009. Vol. 92. P. 955 – 958. DOI: 10.1111/j.1551-2916.2009.02984.xLufaso M. W., Vanderah T. A., Pazos I. M., et al. Phase formation, crystal chemistry, and properties in the system Bi2O3 – Fe2O3 – Nb2O5 / Journal of Solid State Chemistry. 2006. Vol. 179. P. 3900 – 3910. DOI: 10.1016/j.jssc.2006.08.036Lufaso M. W., Vanderah T. A., Pazos I. M., et al. Phase formation, crystal chemistry, and properties in the system Bi2O3 – Fe2O3 – Nb2O5 / Journal of Solid State Chemistry. 2006. Vol. 179. P. 3900 – 3910. DOI: 10.1016/j.jssc.2006.08.036Vanderah T. A., Lufaso M. W., Adler A. U., et al. Subsolidus phase equilibria and properties in the system Bi2O3: Mn2O3 ± x:Nb2O5 / Journal of Solid State Chemistry. 2006. Vol. 179. P. 3467 – 3477. DOI: 10.1016/j.jssc.2006.07.014Vanderah T. A., Lufaso M. W., Adler A. U., et al. Subsolidus phase equilibria and properties in the system Bi2O3: Mn2O3 ± x:Nb2O5 / Journal of Solid State Chemistry. 2006. Vol. 179. P. 3467 – 3477. DOI: 10.1016/j.jssc.2006.07.014Rylchenko E. P., Makeev B. A., Sivkov D. V., et al. Features of phase formation of pyrochlore-type Bi2Cr1/6Mn1/6Fe1/6Co1/6Ni1/6Cu1/6Ta2O9+Δ / Letters on Materials. 2022. Vol. 12. P. 486 – 492. DOI: 10.22226/2410-3535-2022-4-486-492Rylchenko E. P., Makeev B. A., Sivkov D. V., et al. Features of phase formation of pyrochlore-type Bi2Cr1/6Mn1/6Fe1/6Co1/6Ni1/6Cu1/6Ta2O9+Δ / Letters on Materials. 2022. Vol. 12. P. 486 – 492. DOI: 10.22226/2410-3535-2022-4-486-492Zhuk N. A., Makeev B. A., Krzhizhanovskaya M. G., et al. Features of the phase formation of Cr/Mn/Fe/Co/Ni/Cu codoped bismuth niobate pyrochlore / Crystals. 2023. Vol. 13. P. 1202. DOI: 10.3390/cryst13081202Zhuk N. A., Makeev B. A., Krzhizhanovskaya M. G., et al. Features of the phase formation of Cr/Mn/Fe/Co/Ni/Cu codoped bismuth niobate pyrochlore / Crystals. 2023. Vol. 13. P. 1202. DOI: 10.3390/cryst13081202Parshukova K. N., Sekushin N. A., Makeev B. A., et al. Synthesis and dielectric properties, XPS spectroscopy study of high-entropy pyrochlore / Letters on Materials. 2022. Vol. 12. P. 469 – 474. DOI: 10.22226/2410-3535-2022-4-469-474Parshukova K. N., Sekushin N. A., Makeev B. A., et al. Synthesis and dielectric properties, XPS spectroscopy study of high-entropy pyrochlore / Letters on Materials. 2022. Vol. 12. P. 469 – 474. DOI: 10.22226/2410-3535-2022-4-469-474Sukhanov K. S., Gilev A. R., Kiselev E. A., et al. Functional properties and structure-size factor in La1.4A0.6Ni0.6Fe0.4O4+δ (A = Ca, Sr, Ba) / Journal of Alloys and Compounds. 2024. Vol. 990. Art. 174369. DOI: 10.1016/j.jallcom.2024.174369Sukhanov K. S., Gilev A. R., Kiselev E. A., et al. Functional properties and structure-size factor in La1.4A0.6Ni0.6Fe0.4O4+δ (A = Ca, Sr, Ba) / Journal of Alloys and Compounds. 2024. Vol. 990. Art. 174369. DOI: 10.1016/j.jallcom.2024.174369Aksenova T. V., Mysik D. K., Cherepanov V. A. Crystal structure and properties of Gd1 – xSrxCo1 – yFeyO3 – δ oxides as promising materials for catalytic and SOFC application / Catalysts. 2022. Vol. 12. P. 1344. DOI: 10.3390/catal12111344Aksenova T. V., Mysik D. K., Cherepanov V. A. Crystal structure and properties of Gd1 – xSrxCo1 – yFeyO3 – δ oxides as promising materials for catalytic and SOFC application / Catalysts. 2022. Vol. 12. P. 1344. DOI: 10.3390/catal12111344Gilev A. R., Kiselev E. A., Sukhanov K. S., et al. Evaluation of La2 – x(Ca/Sr)xNi1 – yFeyO4+δ (x = 0.5, 0.6; y = 0.4, 0.5) as cathodes for proton-conducting SOFC based on lanthanum tungstate / Electrochimica Acta. 2022. Vol. 421. Art. 140479. DOI: 10.1016/j.electacta.2022.140479Gilev A. R., Kiselev E. A., Sukhanov K. S., et al. Evaluation of La2 – x(Ca/Sr)xNi1 – yFeyO4+δ (x = 0.5, 0.6; y = 0.4, 0.5) as cathodes for proton-conducting SOFC based on lanthanum tungstate / Electrochimica Acta. 2022. Vol. 421. Art. 140479. DOI: 10.1016/j.electacta.2022.140479Shevchenko V. A., Komayko A. I., Sivenkova E. V., et al. Effect of Ni/Fe/Mn ratio on electrochemical properties of the O3 – NaNi1 – x – yFexMnyO2 (0.25 ≤ x, y ≤ 0.75) cathode materials for Na-ion batteries / Journal of Power Sources. 2024. Vol. 596. Art. 234092. DOI: 10.1016/j.jpowsour.2024.234092Shevchenko V. A., Komayko A. I., Sivenkova E. V., et al. Effect of Ni/Fe/Mn ratio on electrochemical properties of the O3 – NaNi1 – x – yFexMnyO2 (0.25 ≤ x, y ≤ 0.75) cathode materials for Na-ion batteries / Journal of Power Sources. 2024. Vol. 596. Art. 234092. DOI: 10.1016/j.jpowsour.2024.234092Akselrud L. G., Grin Yu. N., Zavalij P. Yu., et al. CSD-universal program package for single crystal or powder structure data treatment / Thes. Rep. XII Eur. Crystallogr. Meet. 1989. Vol. 12. P. 155.Akselrud L. G., Grin Yu. N., Zavalij P. Yu., et al. CSD-universal program package for single crystal or powder structure data treatment / Thes. Rep. XII Eur. Crystallogr. Meet. 1989. Vol. 12. P. 155.Zhdanov P. A., Seregina I. F., Osipov K. B., et al. X-Ray Spectrpscopic Determination of Different Forms of Vanadium, Iron and Manganese in the Samples of Slag and Batch of Vanadium Production / Industr. Lab. Mater. Diagn. 2016. Vol. 82. No. 3. P. 13 – 18 [in Russian].Zhdanov P. A., Seregina I. F., Osipov K. B., et al. X-Ray Spectrpscopic Determination of Different Forms of Vanadium, Iron and Manganese in the Samples of Slag and Batch of Vanadium Production / Industr. Lab. Mater. Diagn. 2016. Vol. 82. No. 3. P. 13 – 18 [in Russian].Shannon R. D. Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides / Acta Crystallographica Section A: Foundations and Advances. 1976. Vol. 32. P. 751 – 767. DOI: 10.1107/s0567739476001551Shannon R. D. Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides / Acta Crystallographica Section A: Foundations and Advances. 1976. Vol. 32. P. 751 – 767. DOI: 10.1107/s0567739476001551Zhuk N. A., Krzhizhanovskaya M. G., Koroleva A. V., et al. Thermal expansion, XPS spectra and structural and electrical properties of a new Bi2NiTa2O9 pyrochlore / Inorganic Chemistry. 2021. Vol. 60. P. 4924 – 4934. DOI: 10.1021/acs.inorgchem.1c00007Zhuk N. A., Krzhizhanovskaya M. G., Koroleva A. V., et al. Thermal expansion, XPS spectra and structural and electrical properties of a new Bi2NiTa2O9 pyrochlore / Inorganic Chemistry. 2021. Vol. 60. P. 4924 – 4934. DOI: 10.1021/acs.inorgchem.1c00007Zhuk N. A., Krzhizhanovskaya M. G., Sekushin N. A., et al. Crystal structure, dielectric and thermal properties of cobalt doped bismuth tantalate pyrochlore / Journal of Materials Research and Technology. 2023. Vol. 22. P. 1791 – 1799. DOI: 10.1016/j.jmrt.2022.12.059Zhuk N. A., Krzhizhanovskaya M. G., Sekushin N. A., et al. Crystal structure, dielectric and thermal properties of cobalt doped bismuth tantalate pyrochlore / Journal of Materials Research and Technology. 2023. Vol. 22. P. 1791 – 1799. DOI: 10.1016/j.jmrt.2022.12.059Hassel M., Freund H.-J. High resolution XPS study of a thin CoO(111) film grown on Co(0001) / Surface Science Spectra. 1996. Vol. 4. P. 273 – 278. DOI: 10.1116/1.1247797Hassel M., Freund H.-J. High resolution XPS study of a thin CoO(111) film grown on Co(0001) / Surface Science Spectra. 1996. Vol. 4. P. 273 – 278. DOI: 10.1116/1.1247797Vanderah T., Siegrist T., Lufaso M., et al. Phase formation and properties in the system Bi2O3:2CoO1 + x:Nb2O5 / European Journal of Inorganic Chemistry. 2006. Vol. 2006. P. 4908 – 4914. DOI: 10.1002/ejic.200600661Vanderah T., Siegrist T., Lufaso M., et al. Phase formation and properties in the system Bi2O3:2CoO1 + x:Nb2O5 / European Journal of Inorganic Chemistry. 2006. Vol. 2006. P. 4908 – 4914. DOI: 10.1002/ejic.200600661Mansour A. N., Melendres C. A. Characterization of Ni2O3 · 6H2O by XPS / Surface Science Spectra. 1994. Vol. 3. P. 263 – 270. DOI: 10.1116/1.1247754Mansour A. N., Melendres C. A. Characterization of Ni2O3 · 6H2O by XPS / Surface Science Spectra. 1994. Vol. 3. P. 263 – 270. DOI: 10.1116/1.1247754Barreca D., Gasparotto A., Tondello E. CVD Cu2O and CuO nanosystems Characterized by XPS / Surface Science Spectra. 2007. Vol. 14. P. 41 – 51. DOI: 10.1116/11.20080701Barreca D., Gasparotto A., Tondello E. CVD Cu2O and CuO nanosystems Characterized by XPS / Surface Science Spectra. 2007. Vol. 14. P. 41 – 51. DOI: 10.1116/11.20080701

The authors declare that there are no conflicts of interest present.