Potential-induced restructuring dynamics of ionic liquids on a gold electrode: Steric effect of constituent ions studied by surface-enhanced infrared absorption spectroscopy

Motobayashi, Kenta; Nishi, Naoya; Inoue, Yuki; Minami, Kazuya; Sakka, Tetsuo; Osawa, Masatoshi

Potential-induced restructuring dynamics of ionic liquids on a gold electrode: Steric effect of constituent ions studied by surface-enhanced infrared absorption spectroscopy

Motobayashi, Kenta; Nishi, Naoya; Inoue, Yuki et al.

Journal of electroanalytical chemistry, 2017, 800, 126-133

Permalink : https://hdl.handle.net/2115/75313

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アクセス権	open access
URI	https://hdl.handle.net/2115/75313
タイトル	Potential-induced restructuring dynamics of ionic liquids on a gold electrode: Steric effect of constituent ions studied by surface-enhanced infrared absorption spectroscopy
著者	Motobayashi, Kenta ; Nishi, Naoya ; Inoue, Yuki ; Minami, Kazuya ; Sakka, Tetsuo ; Osawa, Masatoshi
著者名 Motobayashi, Kenta
著者名 Nishi, Naoya
著者名 Inoue, Yuki
著者名 Minami, Kazuya
著者名 Sakka, Tetsuo
e-Rad_Researcher 00108466 著者名 Osawa, Masatoshi
言語	英語
キーワード	Spectroelectrochemistry
	Vibrational spectroscopy
	Solid/liquid interface
	Ionic liquid
	Electrical double layer
	Surface science
発行日	2017-09-01
出版者	Elsevier
収録物名	Journal of electroanalytical chemistry
巻(号)	800
ページ	126-133
抄録	The structure of the interface between room temperature ionic liquids (RTILs) and an Au electrode changes with applied potential to compensate the charge on the electrode surface. The dynamics of the restructuring of RTILs triggered by the change in potential has been investigated by using surface-enhanced infrared absorption spectroscopy (SEIRAS). To elucidate the effect of steric hindrance of constituent ions on the potential-dependent dynamics, RTILs composed of differently sized ions are examined: imidazolium cations and bis(perfluoroalicylsulfonyl)amide anions with different (perfluoro)alkyl chain length, or tetrafluoroborate anion. The high interface selectivity and sensitivity of SEIRAS enables in-situ, real time observation of dynamic behaviors of both anions and cations during potential scans or steps. During potential scans for RTILs composed of sufficiently large ions (all the RTILs examined in the present study except for that includes BFT), a fast, barrier-less change in local ion concentration occurs in the overlayers first, and then a slow cation-anion replacement occurs in the first ionic layer directly contacting with the electrode surface when an overpotential exceeding a critical value is applied. SEIRAS reveals hysteretic changes of the interfacial structure arising from the ion replacement in the first ionic layer. Potential dependent SEIRAS measurements for RTILs with different ion sizes highlight the significance of steric hindrance of ions for the ion replacement in the first layer. (C) 2017 Elsevier B.V. All rights reserved.
資源タイプ	学術雑誌論文
出版タイプ	Accepted Manuscript
権利情報	Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International
権利情報	© 2017. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/
PISSN	1572-6657
関連情報 (isVersionOf)	出版社版DOI https://doi.org/10.1016/j.jelechem.2017.02.049