XPS and NEXAFS Characterization of Mg/Zn and Mn Codoped Bismuth Tantalate Pyrochlores
Two series of the bismuth tantalate pyrochlore samples, codoped with Mg,Mn and Zn,Mn, were synthesized via solid-phase reaction. It was established that the Bi<sub>2</sub>Mg(Zn)<sub>x</sub>Mn<sub>1−x</sub>Ta<sub>2</sub>O<sub>9.5−Δ</sub> (x...
| Main Authors: | , , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2024-02-01
|
| Series: | Inorganics |
| Subjects: | |
| Online Access: | https://www.mdpi.com/2304-6740/12/3/74 |
| _version_ | 1797240620845105152 |
|---|---|
| author | Nadezhda A. Zhuk Boris A. Makeev Aleksandra V. Koroleva Aleksey M. Lebedev Olga V. Petrova Sergey V. Nekipelov Viktor N. Sivkov |
| author_facet | Nadezhda A. Zhuk Boris A. Makeev Aleksandra V. Koroleva Aleksey M. Lebedev Olga V. Petrova Sergey V. Nekipelov Viktor N. Sivkov |
| author_sort | Nadezhda A. Zhuk |
| collection | DOAJ |
| description | Two series of the bismuth tantalate pyrochlore samples, codoped with Mg,Mn and Zn,Mn, were synthesized via solid-phase reaction. It was established that the Bi<sub>2</sub>Mg(Zn)<sub>x</sub>Mn<sub>1−x</sub>Ta<sub>2</sub>O<sub>9.5−Δ</sub> (x = 0.3; 0.5; 0.7) samples contain the main phase of cubic pyrochlore (sp. gr. Fd-3m) and an admixture of triclinic BiTaO<sub>4</sub> (sp. gr. P-1). In both sets, the amount of BiTaO<sub>4</sub> is proportional to the amount of manganese doping, however, zinc-containing samples have a higher level of impurities than magnesium-containing ones. The unit cell parameter of the Zn,Mn codoped bismuth tantalate phase increases with an increasing content of zinc ions in the samples from 10.4895(5) (x = 0.3) to 10.5325(5) Å (x = 0.7). The unit cell parameter of Mg,Mn codoped bismuth tantalate pyrochlores increases uniformly with an increasing index x(Mg) from 10.4970(8) at x = 0.3 to 10.5248(8) Å at x = 0.7, according to the Vegard rule. The NEXAFS and XPS data showed that the ions were found to have oxidation states of Bi(+3), Ta(+5), Zn(+2) and Mg(+2). In the Ta 4f XPS spectrum of both series of samples, a low energy shift of the absorption band characteristic of tantalum ions with an effective charge of (+5-δ) was observed. The XPS spectra of Bi4f7/2 and Bi4f5/2 also show a shift of bands towards lower energies which is attributed to the presence of some low-charge ions of transition elements in the bismuth position. The NEXAFS spectroscopy data showed that manganese ions in both series of samples have predominantly 2+ and 3+ oxidation states. XPS data indicate that in zinc-containing preparations the proportion of oxidized manganese ions is higher than in magnesium-containing ones. |
| first_indexed | 2024-04-24T18:10:20Z |
| format | Article |
| id | doaj.art-77c3473042514b0eb370d3ba91eaff82 |
| institution | Directory Open Access Journal |
| issn | 2304-6740 |
| language | English |
| last_indexed | 2024-04-24T18:10:20Z |
| publishDate | 2024-02-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Inorganics |
| spelling | doaj.art-77c3473042514b0eb370d3ba91eaff822024-03-27T13:47:05ZengMDPI AGInorganics2304-67402024-02-011237410.3390/inorganics12030074XPS and NEXAFS Characterization of Mg/Zn and Mn Codoped Bismuth Tantalate PyrochloresNadezhda A. Zhuk0Boris A. Makeev1Aleksandra V. Koroleva2Aleksey M. Lebedev3Olga V. Petrova4Sergey V. Nekipelov5Viktor N. Sivkov6Institute of Natural Sciences, Syktyvkar State University, Oktyabrsky Prospect, 55, Syktyvkar 167001, RussiaInstitute of Geology of the Komi Science Center UB RAS, Pervomaiskaya St. 48, Syktyvkar 167982, RussiaResearch Park, Saint Petersburg State University, Saint Petersburg 199034, RussiaNational Research Center, Kurchatov Institute, 1 Akad. Kurchatova Sq., Moscow 123182, RussiaInstitute of Physics and Mathematics, Komi Science Centre, Ural Branch of the Russian Academy of Sciences, Syktyvkar 167982, RussiaInstitute of Physics and Mathematics, Komi Science Centre, Ural Branch of the Russian Academy of Sciences, Syktyvkar 167982, RussiaInstitute of Physics and Mathematics, Komi Science Centre, Ural Branch of the Russian Academy of Sciences, Syktyvkar 167982, RussiaTwo series of the bismuth tantalate pyrochlore samples, codoped with Mg,Mn and Zn,Mn, were synthesized via solid-phase reaction. It was established that the Bi<sub>2</sub>Mg(Zn)<sub>x</sub>Mn<sub>1−x</sub>Ta<sub>2</sub>O<sub>9.5−Δ</sub> (x = 0.3; 0.5; 0.7) samples contain the main phase of cubic pyrochlore (sp. gr. Fd-3m) and an admixture of triclinic BiTaO<sub>4</sub> (sp. gr. P-1). In both sets, the amount of BiTaO<sub>4</sub> is proportional to the amount of manganese doping, however, zinc-containing samples have a higher level of impurities than magnesium-containing ones. The unit cell parameter of the Zn,Mn codoped bismuth tantalate phase increases with an increasing content of zinc ions in the samples from 10.4895(5) (x = 0.3) to 10.5325(5) Å (x = 0.7). The unit cell parameter of Mg,Mn codoped bismuth tantalate pyrochlores increases uniformly with an increasing index x(Mg) from 10.4970(8) at x = 0.3 to 10.5248(8) Å at x = 0.7, according to the Vegard rule. The NEXAFS and XPS data showed that the ions were found to have oxidation states of Bi(+3), Ta(+5), Zn(+2) and Mg(+2). In the Ta 4f XPS spectrum of both series of samples, a low energy shift of the absorption band characteristic of tantalum ions with an effective charge of (+5-δ) was observed. The XPS spectra of Bi4f7/2 and Bi4f5/2 also show a shift of bands towards lower energies which is attributed to the presence of some low-charge ions of transition elements in the bismuth position. The NEXAFS spectroscopy data showed that manganese ions in both series of samples have predominantly 2+ and 3+ oxidation states. XPS data indicate that in zinc-containing preparations the proportion of oxidized manganese ions is higher than in magnesium-containing ones.https://www.mdpi.com/2304-6740/12/3/74pyrochloreZnMgMn dopingBiTaO<sub>4</sub>XPS and NEXAFS spectroscopy |
| spellingShingle | Nadezhda A. Zhuk Boris A. Makeev Aleksandra V. Koroleva Aleksey M. Lebedev Olga V. Petrova Sergey V. Nekipelov Viktor N. Sivkov XPS and NEXAFS Characterization of Mg/Zn and Mn Codoped Bismuth Tantalate Pyrochlores Inorganics pyrochlore Zn Mg Mn doping BiTaO<sub>4</sub> XPS and NEXAFS spectroscopy |
| title | XPS and NEXAFS Characterization of Mg/Zn and Mn Codoped Bismuth Tantalate Pyrochlores |
| title_full | XPS and NEXAFS Characterization of Mg/Zn and Mn Codoped Bismuth Tantalate Pyrochlores |
| title_fullStr | XPS and NEXAFS Characterization of Mg/Zn and Mn Codoped Bismuth Tantalate Pyrochlores |
| title_full_unstemmed | XPS and NEXAFS Characterization of Mg/Zn and Mn Codoped Bismuth Tantalate Pyrochlores |
| title_short | XPS and NEXAFS Characterization of Mg/Zn and Mn Codoped Bismuth Tantalate Pyrochlores |
| title_sort | xps and nexafs characterization of mg zn and mn codoped bismuth tantalate pyrochlores |
| topic | pyrochlore Zn Mg Mn doping BiTaO<sub>4</sub> XPS and NEXAFS spectroscopy |
| url | https://www.mdpi.com/2304-6740/12/3/74 |
| work_keys_str_mv | AT nadezhdaazhuk xpsandnexafscharacterizationofmgznandmncodopedbismuthtantalatepyrochlores AT borisamakeev xpsandnexafscharacterizationofmgznandmncodopedbismuthtantalatepyrochlores AT aleksandravkoroleva xpsandnexafscharacterizationofmgznandmncodopedbismuthtantalatepyrochlores AT alekseymlebedev xpsandnexafscharacterizationofmgznandmncodopedbismuthtantalatepyrochlores AT olgavpetrova xpsandnexafscharacterizationofmgznandmncodopedbismuthtantalatepyrochlores AT sergeyvnekipelov xpsandnexafscharacterizationofmgznandmncodopedbismuthtantalatepyrochlores AT viktornsivkov xpsandnexafscharacterizationofmgznandmncodopedbismuthtantalatepyrochlores |