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Valence state of Mn/Cr/Co/Cu cations in multi-element pyrochlores
Russian version
Nekipelov S. V.1, Sivkov V. N. 1, Koroleva A. V.2, Zhuk N. A.
1Komi Science Centre of the Ural Division of the Russian Academy of Sciences, Syktyvkar, Russia
2St. Petersburg State University, St. Petersburg, Russia
Email: nekipelovsv@mail.ru
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Three-component single-phase cubic pyrochlores Bi2-xCr1/3Mn1/3(Co/Cu)1/3Nb2O9-Δ (sp. gr. Fd-3m) were synthesized for the first time by the solid-phase reaction method. The unit cell parameter, depending on the chemical composition, changes from 10.4546(2) to 10.4832(2) A. The chemical state of transition element cations in pyrochlores was characterized by X-ray photoelectron spectroscopy (XPS). The parameters of the XPS spectra of Bi4f, Nb3d, Co2p, Cu2p, Mn2p, Cr2p for mixed pyrochlores are compared with the parameters of transition element oxides in different oxidation states. For complex pyrochlores, a characteristic shift of Bi4f and Nb3d spectra to lower energies by 0.1-0.2 and 0.6-0.65 eV, respectively, is observed. According to XPS and NEXAFS spectra, chromium, cobalt and copper atoms are in the charge state of Cr3+, Co2+ and Cu2+, and manganese atoms are in the mixed charge state of Mn2+/Mn3. Keywords: synthesis, pyrochlore, XPS, 3d elements, oxidation state.
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