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Electroseparation of zinc(II) from uranium(III) prepared by reduction of uranium(IV) with zinc amalgam in dimethylformamide

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Abstract

The Electroseparation of zinc(II) from a solution of uranium(III) generated by the reduction of uranium(IV) triflate (U(OTf)4) with zinc amalgam (Zn(Hg)) was studied to establish a convenient route to the precursors of organic uranium(III) compounds. Specifically, the electrode reactions of U(OTf)4 in N,N-dimethylformamide on mercury (Hg) and Zn(Hg) electrodes were probed by voltammetry and bulk electrolysis measurements. The voltammograms recorded on the former electrode showed three cathodic waves assigned to the reduction of a uranium(IV) solvate complex (− 1.48 V), the reduction of [U(OTf)]3+ (− 1.81 V), and uranium amalgamation (− 2.65 V). On the latter electrode, the first cathodic wave was masked, as it was located at the potential of zinc amalgamation. Bulk electrolysis experiments revealed that for both Hg and Zn(Hg), the working electrode potential featured a plateau around − 2.3 V, which was not observed in the corresponding voltammograms and was related to the degradation of uranium(III) based on spectroscopic observations. The Electroseparation of zinc(II) from the uranium(III) solution on Zn(Hg) was successfully (highest coulombic efficiency = 0.81, final zinc(II) separation ratio = 93.4%) carried out after the reduction of U(OTf)4 by Zn(Hg).

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Acknowledgements

The author would like to express great acknowledgements to Prof. Tomoo Yamamura (Inst. for Integrated Radiation and Nuclear Science, Kyoto Univ.) and late associate Prof. Isamu Satoh for their kind encouragements and supports. This work was partly supported by JSPS KAKENHI [Grant No. 19760607].

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  1. Institute for Materials Research, Tohoku University, Sendai, Miyagi, 980-8577, Japan

    Kenji Shirasaki

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Shirasaki, K. Electroseparation of zinc(II) from uranium(III) prepared by reduction of uranium(IV) with zinc amalgam in dimethylformamide. J Appl Electrochem 52, 1101–1108 (2022). https://doi.org/10.1007/s10800-022-01698-7

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