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Interfacial Structure at the Quaternary Ammonium-Based Ionic Liquids|Gold Electrode Interface Probed by Surface-Enhanced Infrared Absorption Spectroscopy: Anion Dependence of the Cationic Behavior
journal contribution
posted on 2016-12-21, 00:00 authored by Naoya Nishi, Kazuya Minami, Kenta Motobayashi, Masatoshi Osawa, Tetsuo SakkaThe
interfacial structure at the quaternary ammonium-based ionic
liquids(ILs)|gold(Au) electrode interface has been studied using surface-enhanced
infrared absorption spectroscopy (SEIRAS). Four anions, bis(perfluoroalkanesulfonyl)amide
(CnCnN–; n = 0, 1, 2, 4), have been combined
with a quaternary ammonium cation, trioctylmethylammonium (N8881+), to investigate
the influence of the perfluoroalkyl chain length of the anion on the
behavior of the quaternary ammonium cation at the interface. In addition,
to investigate the effect of the alkyl chain length of the quaternary
ammonium cations on the cationic behavior, we have also combined a
cation with a shorter alkyl chain, tributylmethylammonium (N4441+) with C1C1N–. Thus, we have performed
SEIRAS measurements at the Au interface of five ILs: [N8881+][CnCnN–] (n = 0, 1, 2, 4) and [N4441+][C1C1N–]. The four CH stretching bands originating from the quaternary ammonium
cations have been individually analyzed, enabling us to reveal the
behavior of the quaternary ammonium cations at the interface. The
cationic behavior is found to dramatically depend not only on the
alkyl chain length but also on the perfluoroalkyl chain length of
the counterion. For [N8881+][C4C4N–] and [N8881+][C2C2N–], octyl chains of
N8881+ cannot
reach the Au electrode surface at positive potentials because the
bulky anions in the first ionic layer on the electrode surface block
the approach. Conversely, for ILs with the smaller anions ([N8881+][C1C1N–] and [N8881+][C0C0N–]), octyl chains of N8881+ can penetrate into a space in the first ionic
layer of small anions. The butyl chains of N4441+ in [N4441+][C1C1N–] cannot reach the surface at positive potentials even across the
first ionic layer of the small anions because of their relatively
short alkyl chain length.