掺钴钽酸铋镁热裂解物的 NEXAFS 和 XPS 研究

Q3 Chemistry
Chemistry Pub Date : 2024-04-03 DOI:10.3390/chemistry6020018
N. Zhuk, B. Makeev, A.V. Koroleva, S. Nekipelov, O. V. Petrova
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引用次数: 0

摘要

采用标准陶瓷法首次合成了掺钴的热绿结构钽酸铋镁(sp. gr. Fd-3m)。在 X 射线相分析中发现,当 x < 0.7 时,会形成单相 Bi2Mg1-xCoxTa2O9 样品。然而,当样品中的钴含量越高时,就会检测到杂质相 β-BiTaO4(sp. gr. P-1),其含量与钴的掺杂程度成正比。随着样品中钴离子含量从 10.5412(8) (x = 0.3) 增加到 10.5499(8) Å (x = 0.7),钴、镁共掺杂钽酸铋相的单胞参数均匀增加,这证明了固溶体的形成。样品呈现出多孔的微观结构,由杂乱取向和部分融合的细长晶粒组成,尺寸为 1-2 μm。陶瓷晶粒大小与 n(Mg)/n(Co)比率的关系尚未确定。利用 X 射线光谱法(耳廓 X 射线吸附结构(NEXAFS)和 X 射线光电子能谱(XPS))研究了 Bi2Mg1-xCoxTa2O9 中离子的电荷状态。NEXAFS 和 XPS 数据表明,钴和镁的掺杂并没有改变烧绿石中铋和钽的氧化态,尤其是离子保持了 Bi(+3)、Mg(+2) 和 Ta(+5) 的氧化态。与五价氧化钽 Ta2O5 中的结合能相比,Ta4f-、Ta5p- 和 Ta4d 光谱峰的能量位置具有向低能量移动的特征。向较低能量移动是有效正电荷减少的特征;特别是在我们展示的 Ta4f 和 Ta4d 光谱中,这种能量移动为 ΔE = 0.65 eV,在 Ta4d 边缘区域为-0.55 eV。这反过来又使我们可以假设钽原子具有相同的有效电荷 +(5-δ)。根据 NEXAFS 光谱数据,钴离子的氧化态主要为 2+,部分为 3+。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
NEXAFS and XPS Studies of Co Doped Bismuth Magnesium Tantalate Pyrochlores
Co doped bismuth magnesium tantalate with a pyrochlore structure (sp. gr. Fd-3m) was synthesized for the first time using the standard ceramic method. Single phase Bi2Mg1−xCoxTa2O9 samples were found to be formed when x < 0.7 in the X-ray phase analysis. However, with a higher cobalt content in the samples, the impurity phase β-BiTaO4 (sp. gr. P-1) is detected, and its amount is proportional to the degree of cobalt doping. The formation of solid solutions is evidenced by a uniform increase in the unit cell parameter of the Co,Mg co doped bismuth tantalate phase with an increase in the content of cobalt ions in the samples from 10.5412(8) (x = 0.3) to 10.5499(8) Å (x = 0.7). The samples exhibit a porous microstructure consisting of chaotically oriented and partially fused elongated grains measuring 1–2 μm. The dependence of the ceramic grain size on the n(Mg)/n(Co) ratio was not determined. X-ray spectroscopy (ear dge X-ray bsorption ine tructure (NEXAFS) and X-ray photoelectron spectroscopy (XPS)) was used to study the charge state of ions in Bi2Mg1−xCoxTa2O9. The NEXAFS and XPS data showed that doping with cobalt and magnesium did not change the bismuth and tantalum oxidation states in pyrochlore; in particular, the ions maintained their oxidation states of Bi(+3), Mg(+2) and Ta(+5). The energy position of the peaks of the Ta4f-, Ta5p-, Ta4d spectra had a characteristic shift towards lower energies compared to the binding energy in pentavalent tantalum oxide Ta2O5. A shift towards lower energies is characteristic of a decrease in the effective positive charge; in particular, for the Ta4f and Ta4d spectra we presented, this energy shift was ΔE = 0.65 eV, and in the region of the Ta4d edge—0.55 eV. This in turn allowed for us to assume that tantalum atoms have the same effective charge +(5-δ). The oxidation state of cobalt ions was predominantly 2+ and partially 3+, according to NEXAFS spectroscopy data.
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来源期刊
CiteScore
2.50
自引率
0.00%
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0
审稿时长
11 weeks
期刊介绍: Chemistry—A European Journal is a truly international journal with top quality contributions (2017 ISI Impact Factor: 5.16). It publishes a wide range of outstanding Reviews, Minireviews, Concepts, Full Papers, and Communications from all areas of chemistry and related fields.
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