A long-chain protic ionic liquid inside silica nanopores: enhanced proton mobility due to efficient self-assembly and decoupled proton transport

Nanoscale
Mounesha N GaragaAnna Martinelli

Abstract

We report enhanced protonic and ionic dynamics in an imidazole/protic ionic liquid mixture confined within the nanopores of silica particles. The ionic liquid is 1-octylimidazolium bis(trifluoromethanesulfonyl)imide ([HC8Im][TFSI]), while the silica particles are microsized and characterized by internal well connected nanopores. We demonstrate that the addition of imidazole is crucial to promote a proton motion decoupled from molecular diffusion, which occurs due to the establishment of new N-HN hydrogen bonds and fast proton exchange events in the ionic domains, as evidenced by both infrared and 1H NMR spectroscopy. An additional reason for the decoupled motion of protons is the nanosegregated structure adopted by the liquid imidazole/[HC8Im][TFSI] mixture, with segregated polar and non-polar nano-domains, as clearly shown by WAXS data. This arrangement, promoted by the length of the octyl group and thus by significant chain-chain interactions, reduces the mobility of molecules (Dmol) more than that of protons (DH), which is manifested by DH/Dmol ratios greater than three. Once included into the nanopores of hydrophobic silica microparticles, the nanostructure of the liquid mixture is preserved with slightly larger ionic domai...Continue Reading

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Citations

Mar 23, 2020·The Journal of Chemical Physics·Christian DreßlerDaniel Sebastiani
Apr 19, 2019·Nanomaterials·Teng-Hui WangHai-Chou Chang
May 13, 2021·The Journal of Physical Chemistry. B·Alexandra V BaylesTodd M Squires
Apr 18, 2019·The Journal of Physical Chemistry. B·Iqbaal AbdurrokhmanAnna Martinelli
Apr 16, 2020·Chemical Reviews·Yong-Lei WangMichael D Fayer

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Methods Mentioned

BETA
NMR
infrared spectroscopy
X-ray

Software Mentioned

WaveMetrics
Igor Pro

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