Electrochemical behavior of [UO 2Cl 4] 2- in 1-ethyl-3-methylimidazolium based ionic liquids

Toshinari Ogura, Kotoe Sasaki, Koichiro Takao, Tsuyoshi Arai, Yasuhisa Ikeda

Research output: Contribution to journalArticle

15 Citations (Scopus)

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[UO 2Cl 4] into a mixture of EMICl and EMIBF 4 (50:50 mol%) were measured. As a result, it was confirmed that uranyl species in the mixture of EMICl and EMIBF4 existed as [UO 2Cl 4] 2-. Cyclic voltammograms (CVs) of [UO 2Cl 4] 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 AgNO 3, 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 [UO 2Cl 4] 2- and the standard rate constant were estimated to be 3.7 × 10 -8 cm 2 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, [UO 2Cl 4] 2- + e - = [UO 2Cl 4] 3-. The simulated CVs were found to be consistent with the experimental ones. From these results, it is concluded that [UO 2Cl 4] 2- in the mixture of EMICl and EMIBF 4 is reduced to [UO 2Cl 4] 3- quasi-reversibly at -0.989 V vs. Fc/Fc +.

Original languageEnglish
Pages (from-to)1699-1704
Number of pages6
JournalScience China Chemistry
Volume55
Issue number9
DOIs
Publication statusPublished - 2012 Sep

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Ionic Liquids
Electrodes
Rate constants
Absorption spectra
Wire
Ions
1-ethyl-3-methylimidazolium

Keywords

  • Cyclic voltammetry
  • Electrochemistry
  • Ionic liquids
  • Uranyl chloride

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Electrochemical behavior of [UO 2Cl 4] 2- in 1-ethyl-3-methylimidazolium based ionic liquids. / Ogura, Toshinari; Sasaki, Kotoe; Takao, Koichiro; Arai, Tsuyoshi; Ikeda, Yasuhisa.

In: Science China Chemistry, Vol. 55, No. 9, 09.2012, p. 1699-1704.

Research output: Contribution to journalArticle

Ogura, Toshinari ; Sasaki, Kotoe ; Takao, Koichiro ; Arai, Tsuyoshi ; Ikeda, Yasuhisa. / Electrochemical behavior of [UO 2Cl 4] 2- in 1-ethyl-3-methylimidazolium based ionic liquids. In: Science China Chemistry. 2012 ; Vol. 55, No. 9. pp. 1699-1704.
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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[UO 2Cl 4] into a mixture of EMICl and EMIBF 4 (50:50 mol{\%}) were measured. As a result, it was confirmed that uranyl species in the mixture of EMICl and EMIBF4 existed as [UO 2Cl 4] 2-. Cyclic voltammograms (CVs) of [UO 2Cl 4] 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 AgNO 3, 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 [UO 2Cl 4] 2- and the standard rate constant were estimated to be 3.7 × 10 -8 cm 2 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, [UO 2Cl 4] 2- + e - = [UO 2Cl 4] 3-. The simulated CVs were found to be consistent with the experimental ones. From these results, it is concluded that [UO 2Cl 4] 2- in the mixture of EMICl and EMIBF 4 is reduced to [UO 2Cl 4] 3- quasi-reversibly at -0.989 V vs. Fc/Fc +.",
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AU - Sasaki, Kotoe

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AU - Arai, Tsuyoshi

AU - Ikeda, Yasuhisa

PY - 2012/9

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N2 - 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[UO 2Cl 4] into a mixture of EMICl and EMIBF 4 (50:50 mol%) were measured. As a result, it was confirmed that uranyl species in the mixture of EMICl and EMIBF4 existed as [UO 2Cl 4] 2-. Cyclic voltammograms (CVs) of [UO 2Cl 4] 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 AgNO 3, 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 [UO 2Cl 4] 2- and the standard rate constant were estimated to be 3.7 × 10 -8 cm 2 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, [UO 2Cl 4] 2- + e - = [UO 2Cl 4] 3-. The simulated CVs were found to be consistent with the experimental ones. From these results, it is concluded that [UO 2Cl 4] 2- in the mixture of EMICl and EMIBF 4 is reduced to [UO 2Cl 4] 3- quasi-reversibly at -0.989 V vs. Fc/Fc +.

AB - 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[UO 2Cl 4] into a mixture of EMICl and EMIBF 4 (50:50 mol%) were measured. As a result, it was confirmed that uranyl species in the mixture of EMICl and EMIBF4 existed as [UO 2Cl 4] 2-. Cyclic voltammograms (CVs) of [UO 2Cl 4] 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 AgNO 3, 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 [UO 2Cl 4] 2- and the standard rate constant were estimated to be 3.7 × 10 -8 cm 2 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, [UO 2Cl 4] 2- + e - = [UO 2Cl 4] 3-. The simulated CVs were found to be consistent with the experimental ones. From these results, it is concluded that [UO 2Cl 4] 2- in the mixture of EMICl and EMIBF 4 is reduced to [UO 2Cl 4] 3- quasi-reversibly at -0.989 V vs. Fc/Fc +.

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