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Electrochemical behavior of [UO2Cl4]2− in 1-ethyl-3-methylimidazolium based ionic liquids

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  • Special Topic Nuclear Fuel Cycle Chemistry
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Abstract

In order to examine the chemical form of uranyl species in 1-ethyl-3-methylimidazolium (EMI) based ionic liquids, UV-visible absorption spectra of solutions prepared by dissolving [EMI]2[UO2Cl4] into a mixture of EMICl and EMIBF4 (50:50 mol%) were measured. As a result, it was confirmed that uranyl species in the mixture of EMICl and EMIBF4 existed as [UO2Cl4]2−. Cyclic voltammograms (CVs) of [UO2Cl4]2− in the mixture were measured at 25 °C using a Pt working electrode, a Pt wire counter electrode, and an Ag/Ag+ reference electrode (0.01 M AgNO3, 0.1 M tetrabutylammonium perchlorate in acetonitrile) in a glove box under an Ar atmosphere. Peaks corresponding to one redox couple were observed around −1.05 V (E pc) and −0.92 V (E pa) vs. ferrocene/ferrocenium ion (Fc/Fc+). The potential differences between two peaks (ΔE p) increased from 101 to 152 mV with an increase in the scan rate from 50 to 300 mV s−1, while the (E pc + E pa)/2 value was constant, −0.989 V vs. Fc/Fc+ regardless of the scan rate. Furthermore, the diffusion coefficient of [UO2Cl4]2− and the standard rate constant were estimated to be 3.7 × 10−8 cm2 s−1 and (2.7–2.8) × 10−4 cm s−1 at 25 °C. By using the diffusion coefficient and the standard rate constant, the simulation of CVs was performed based on the reaction, [UO2Cl4]2− + e− = [UO2Cl4]3−. The simulated CVs were found to be consistent with the experimental ones. From these results, it is concluded that [UO2Cl4]2− in the mixture of EMICl and EMIBF4 is reduced to [UO2Cl4]3− quasi-reversibly at −0.989 V vs. Fc/Fc+.

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Authors and Affiliations

  1. Research Laboratory for Nuclear Reactors, Tokyo Institute of Technology, 2-12-1-N1-34 O-okayama, Meguro-ku, Tokyo, 152-8550, Japan

    Toshinari Ogura & Yasuhisa Ikeda

  2. Department of Materials Science, Shibaura Institute of Technology, 3-7-5 Toyosu, Koto-ku, Tokyo, 135-8548, Japan

    Kotoe Sasaki & Tsuyoshi Arai

  3. Department of Materials and Life Science, Seikei University, 3-3-1 Kichijoji-Kitamachi, Musashino-shi, Tokyo, 180-8633, Japan

    Koichiro Takao

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  1. Toshinari Ogura
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Correspondence to Yasuhisa Ikeda.

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Ogura, T., Sasaki, K., Takao, K. et al. Electrochemical behavior of [UO2Cl4]2− in 1-ethyl-3-methylimidazolium based ionic liquids. Sci. China Chem. 55, 1699–1704 (2012). https://doi.org/10.1007/s11426-012-4693-8

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  • DOI: https://doi.org/10.1007/s11426-012-4693-8

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