Understanding Europium and Terbium Speciation and Ion Pairing in Carbonate Complexes Using Advanced Spectroscopy Techniques

IF 2 4区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR
Nicole Hege, Andrew T. Poore, Shane S. Galley, Benjamin J. Reinhart, Jessica A. Jackson, Shiliang Tian, Jenifer C. Shafer
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Abstract

The lanthanide (Ln) elements are critical materials that are typically extracted/mined together. Their separation by use of solvent extraction from acidic media is well known; however, there are few studies in basic media with carbonate anions. We investigated the complexation of Eu(III) and Tb(III) carbonates as solids and solutions in alkaline K2CO3, wherein we sought to access a Tb(IV) carbonate complex through ozonolysis. L3-edge XANES of Eu and Tb carbonate solids, colorless solutions, and a red-hued Tb solution (obtained by ozonolysis) all showed Ln(III) cations. The absence of evidence for a Tb(IV) complex was confirmed through XAS and EPR analyses, despite the solution exhibiting a deep red color. For solids and solutions, EXAFS results indicate molecular Ln(III)-carbonato anions. In terms of the Eu(III) carbonate coordination number, the coordination does not change upon dissolution of the solid sample. Furthermore, EXAFS for the solutions revealed evidence for the association of potassium cations with the Ln(III)-carbonato anions. This direct observation of contact ion pairing by EXAFS at room temperature is rare. The insights into Ln(III) carbonate complexation and solution speciation afforded by XANES-EXAFS, FT-IR, and EPR provides perspectives that serve as benchmarks for future computational and experimental efforts focused on caustic-side solvent extraction of Ln(III) ions.

Abstract Image

Abstract Image

利用先进的光谱技术了解碳酸盐复合物中的铕和铽的配位及离子配对情况
镧系元素(Ln)是通常一起提取/开采的关键材料。通过溶剂萃取法从酸性介质中分离镧系元素已是众所周知的事情,但在含有碳酸盐阴离子的碱性介质中分离镧系元素的研究却很少。我们研究了 Eu(III)和 Tb(III)碳酸盐在碱性 K2CO3 固体和溶液中的络合情况,并试图通过臭氧分解获得 Tb(IV)碳酸盐络合物。Eu 和 Tb 碳酸盐固体、无色溶液和红色 Tb 溶液(通过臭氧分解获得)的 L3 边 XANES 均显示出 Ln(III) 阳离子。尽管溶液呈现出深红色,但通过 XAS 和 EPR 分析证实没有证据表明存在锑(IV)络合物。对于固体和溶液,EXAFS 结果表明存在分子 Ln(III)- 碳酸阴离子。就 Eu(III)碳酸根的配位数而言,固体样品溶解后配位并没有改变。此外,溶液的 EXAFS 显示了钾阳离子与 Ln(III)- 碳酸根阴离子结合的证据。这种在室温下通过 EXAFS 直接观察到接触离子配对的现象非常罕见。通过 XANES-EXAFS、FT-IR 和 EPR 对 Ln(III)碳酸根的络合和溶液分型的深入了解,为今后计算和实验萃取 Ln(III)离子的苛性钠侧溶剂提供了基准。
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来源期刊
European Journal of Inorganic Chemistry
European Journal of Inorganic Chemistry 化学-无机化学与核化学
CiteScore
4.30
自引率
4.30%
发文量
419
审稿时长
1.3 months
期刊介绍: The European Journal of Inorganic Chemistry (2019 ISI Impact Factor: 2.529) publishes Full Papers, Communications, and Minireviews from the entire spectrum of inorganic, organometallic, bioinorganic, and solid-state chemistry. It is published on behalf of Chemistry Europe, an association of 16 European chemical societies. The following journals have been merged to form the two leading journals, European Journal of Inorganic Chemistry and European Journal of Organic Chemistry: Chemische Berichte Bulletin des Sociétés Chimiques Belges Bulletin de la Société Chimique de France Gazzetta Chimica Italiana Recueil des Travaux Chimiques des Pays-Bas Anales de Química Chimika Chronika Revista Portuguesa de Química ACH—Models in Chemistry Polish Journal of Chemistry The European Journal of Inorganic Chemistry continues to keep you up-to-date with important inorganic chemistry research results.
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