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解析硝酸赛弗斯离子液体中铕(III)的配位方式——一项全面的发光光谱研究。

Unraveling the coordination approach of Eu(III) in cyphos nitrate ionic liquid - a comprehensive luminescence spectroscopy study.

作者信息

Rout Alok, Kumar Satendra, Ramanathan N

机构信息

Materials Chemistry & Metal Fuel Cycle Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603 102, India.

Homi Bhabha National Institute, Indira Gandhi Centre for Atomic Research, Kalpakkam, 603102, India.

出版信息

Dalton Trans. 2022 Apr 5;51(14):5534-5545. doi: 10.1039/d2dt00422d.

Abstract

In consideration of the mounting attention drawn by the ionic liquid cyphos 101 (trihexyl(tetradecyl)phosphonium chloride: [P][Cl]) in the recovery of rare earth metals and other valuable species from their waste matrices, an effort was made using luminescence spectroscopy to study the detailed liquid-liquid extraction and coordination behavior of Eu(III) using the nitrate form of cyphos 101 (cyphos nitrate: [P][NO]) in its undiluted form. Eu(III) complexation with [P][NO] at each stage of the extraction process was investigated using the luminescence spectroscopy technique. Various extraction parameters such as aqueous phase acidity, concentrations of ionic liquid extractant and initial Eu(III) ion, extraction time, experimental temperature, were tuned to discover their impact on the complexation process. The uniqueness of the nitrate ion in ionic liquid was explored by comparing the emission patterns of Eu(III) with [P]-based ionic liquids containing different anions. In addition, the affirmative effect of increasing the initial aqueous phase nitrate ion concentration in the coordination process was underscored by comparing the emission patterns in the chloride medium. The luminescence results of the Eu(III)- [P][NO] complex were compared both in unirradiated and irradiated ionic liquid phases. Asymmetry ratio (AR) and lifetime data under each experimental condition were ascertained, thereby revealing the precise nature of complex formation and strength of the metal-solvate species (metal-ligand complex formation) formed. The stripping of the loaded Eu(III) from the [P][NO] phase was established and the results were presented in the form of the emission patterns of Eu(III) in both phases.

摘要

鉴于离子液体Cyphos 101(三己基(十四烷基)氯化鏻:[P][Cl])在从其废料基质中回收稀土金属和其他有价物质方面受到越来越多的关注,我们开展了一项工作,利用发光光谱法研究了未稀释的硝酸形式的Cyphos 101(硝酸Cyphos:[P][NO])对Eu(III)的详细液 - 液萃取和配位行为。在萃取过程的每个阶段,使用发光光谱技术研究了Eu(III)与[P][NO]的络合情况。调整了各种萃取参数,如水相酸度、离子液体萃取剂浓度、初始Eu(III)离子浓度、萃取时间、实验温度,以发现它们对络合过程的影响。通过比较Eu(III)与含有不同阴离子的[P]基离子液体的发射模式,探索了离子液体中硝酸根离子的独特性。此外,通过比较氯化物介质中的发射模式,强调了在配位过程中增加初始水相硝酸根离子浓度的积极作用。比较了未辐照和辐照离子液相中Eu(III)-[P][NO]络合物的发光结果。确定了每种实验条件下的不对称比(AR)和寿命数据,从而揭示了络合物形成的精确性质以及所形成的金属 - 溶剂化物物种(金属 - 配体络合物形成)的强度。确定了从[P][NO]相中负载的Eu(III)的反萃情况,并以两相中Eu(III)的发射模式形式呈现结果。

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