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从氯化物水溶液到离子液体的溶剂萃取过程中铟(III)氯配合物的物种形成

Speciation of indium(iii) chloro complexes in the solvent extraction process from chloride aqueous solutions to ionic liquids.

作者信息

Deferm Clio, Onghena Bieke, Vander Hoogerstraete Tom, Banerjee Dipanjan, Luyten Jan, Oosterhof Harald, Fransaer Jan, Binnemans Koen

机构信息

KU Leuven, Department of Chemistry, Celestijnenlaan 200F, bus 2404, B-3001 Heverlee, Belgium.

Dutch-Belgian Beamline (DUBBLE), ESRF - The European Synchrotron, CS 40220, 38043 Grenoble Cedex 9, France.

出版信息

Dalton Trans. 2017 Mar 27;46(13):4412-4421. doi: 10.1039/c7dt00618g.

Abstract

Most metal extraction studies focus on the kinetics, the maximum loading and the extraction equilibrium, while structural information on the extracted complexes has been limited. This paper concerns the nature of the indium(iii) chloride complexes, present in the organic and aqueous phase during the solvent extraction of indium(iii) from an aqueous HCl solution by undiluted ionic liquids Cyphos IL 101 and Aliquat 336. In an aqueous HCl solution (0-12 M), indium(iii) exists as octahedral mixed complexes, [In(HO)Cl] (0 ≤ n ≤ 6). EXAFS and In NMR were used to characterize these species. The stoichiometric composition of the extracted complexes, which is estimated from viscosity and maximum loading studies and confirmed by EXAFS, is unaffected by the HCl concentration in the aqueous phase. Indium(iii) is present in the ionic liquid phase as the tetrahedral [InCl] complex. Based on the speciation results an extraction mechanism is proposed.

摘要

大多数金属萃取研究集中在动力学、最大负载量和萃取平衡方面,而关于萃取络合物的结构信息却很有限。本文关注在通过未稀释的离子液体Cyphos IL 101和Aliquat 336从盐酸水溶液中萃取铟(III)的过程中,有机相和水相中存在的氯化铟(III)络合物的性质。在盐酸水溶液(0 - 12 M)中,铟(III)以八面体混合络合物[In(HO)ₙCl₆₋ₙ] (0 ≤ n ≤ 6)的形式存在。采用扩展X射线吸收精细结构谱(EXAFS)和铟核磁共振(In NMR)对这些物种进行表征。从粘度和最大负载量研究估算并经EXAFS证实的萃取络合物的化学计量组成,不受水相中盐酸浓度的影响。铟(III)在离子液体相中以四面体[InCl₄]络合物的形式存在。基于物种形成结果提出了一种萃取机理。

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