Microscopic Insights into Extraction Mechanism of Copper(II) in Ammoniacal Solutions Studied by X-ray Absorption Spectroscopy and Density Functional Theory Calculation

被引：15

作者：

Hu, Jiugang ^{[1
,2
]}

Chen, Qiyuan ^{[1
,2
]}

Hu, Huiping ^{[1
,2
]}

Jiang, Zheng ^{[3
]}

Wang, Duo ^{[1
]}

Wang, Shubin ^{[1
]}

Li, Yaomin ^{[1
]}

机构：

[1] Cent South Univ, Coll Chem & Chem Engn, Changsha 410083, Hunan, Peoples R China

[2] Cent South Univ, Key Lab Resources Chem Nonferrous Met, Minist Educ, Changsha 410083, Peoples R China

[3] Chinese Acad Sci, Shanghai Inst Appl Phys, Shanghai Synchrotron Radiat Facil, Shanghai 201204, Peoples R China

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2013年 / 117卷 / 47期

基金：

中国国家自然科学基金;

关键词：

SULFATE-SOLUTION; COORDINATION; SOLVATION; COMPLEXES; CU(II); SPECIATION; RECOVERY; CHLORIDE; CU2+; IONS;

D O I：

10.1021/jp404768e

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

A microscopic investigation on the extraction process of copper(II) in ammoniacal solutions has been performed by X-ray absorption spectroscopy (XAS) and density functional theory (DFT) calculation. The structural change of copper(II) species in ammoniacal solution has been derived from X-ray absorption near-edge spectroscopy (XANES) by principal component analysis and linear combination fitting. It was found that the coordination structure of the extracted copper complex in the organic phases is planar square and independent of the aqueous pH, whereas the geometries of copper(II) species in ammoniacal solutions changed from axially elongated octahedron to distorted planar square with increase of pH. The coordination geometry and structural parameters of copper(II) species were further obtained by extended X-ray absorption fine structure (EXAFS) fitting and DFT calculation with the B3LYP functional. These results reveal that the formation of tetracoordinated copper(II) ammine species can evidently inhibit the copper extraction reaction. Thus, the extraction mechanism of copper(II) in ammoniacal solutions has been elucidated in view of the microscopic structural aspects of copper species in both organic phase and ammoniacal solutions.

引用

页码：12280 / 12287

页数：8

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