MISC

2003年5月

Bronsted acid-base ionic liquids as proton-conducting nonaqueous electrolytes

JOURNAL OF PHYSICAL CHEMISTRY B
  • A Noda
  • ,
  • AB Susan
  • ,
  • K Kudo
  • ,
  • S Mitsushima
  • ,
  • K Hayamizu
  • ,
  • M Watanabe

107
17
開始ページ
4024
終了ページ
4033
記述言語
英語
掲載種別
書評論文,書評,文献紹介等
DOI
10.1021/jp022347p
出版者・発行元
AMER CHEMICAL SOC

A new series of Bronsted acid-base ionic liquids were derived from the controlled combination of a monoprotonic acid with an organic base under solvent-free conditions. Appropriate amounts of solid bis(trifluoromethanesulfonyl)amide (HTFSI) and solid imidazole (Im) were mixed at various molar ratios to have compositions varying from an equimolar salt to HTFSI- or Im-rich conditions. The mixture at equivalent molar ratio formed a protic neutral salt with a melting point of 73 degreesC, which was thermally stable at temperatures even above 300 degreesC. The melting points of other compositions were lower than those of the equimolar salt and Im or HTFSI, giving eutectics between the equimolar salt and HTFSI or Im. Some of the compositions with certain molar ratios of Im and HTFSI were liquid at room temperature. For Im excess compositions, the conductivity was found to increase with increasing Im mole fraction, and the H-1 NMR chemical shift of the proton attached to the nitrogen atom of Im was shifted to a lower magnetic field. On the contrary, the conductivity decreased with increasing HTFSI mole fraction, and the H-1 NMR chemical shift of the proton attached to the TFSI imide anion also shifted to a higher magnetic field. Self-diffusion coefficients, measured by pulsed-gradient spin-echo NMR (PGSE-NMR) methods in Im- or HTFSI-rich compositions, indicated that fast proton exchange reactions between the protonated Im cation and Im take place in excess Im. The proton conduction follows a combination of Grotthuss- and vehicle-type mechanisms. Direct current polarization measurements were used for the confirmation of proton conduction in Im-rich compositions. Furthermore, reduction of molecular oxygen could be observed at the interface between a Pt electrode and these ionic liquids. This introduces the Bronsted acid-base ionic liquid system as a new candidate for proton conductor such as a fuel cell electrolyte to operate under anhydrous conditions and at elevated temperature.

リンク情報
DOI
https://doi.org/10.1021/jp022347p
Web of Science
https://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=JSTA_CEL&SrcApp=J_Gate_JST&DestLinkType=FullRecord&KeyUT=WOS:000182491000005&DestApp=WOS_CPL
ID情報
  • DOI : 10.1021/jp022347p
  • ISSN : 1520-6106
  • Web of Science ID : WOS:000182491000005

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