title: Microscopic insights into extraction mechanism of copper(II) in ammoniacal solutions studied by X-ray absorption spectroscopy and density functional theory calculation.
abstract: 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.
authors.affiliation: College of Chemistry and Chemical Engineering, Central South University , Changsha 410083, China .
authors.forename: Jiugang
authors.initials: J
authors.lastname: Hu
authors.forename: Qiyuan
authors.initials: Q
authors.lastname: Chen
authors.forename: Huiping
authors.initials: H
authors.lastname: Hu
authors.forename: Zheng
authors.initials: Z
authors.lastname: Jiang
authors.forename: Duo
authors.initials: D
authors.lastname: Wang
authors.forename: Shubin
authors.initials: S
authors.lastname: Wang
authors.forename: Yaomin
authors.initials: Y
authors.lastname: Li