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Surface effects on the structure and mobility of the ionic liquid C(6)C(1)ImTFSI in silica gels

Moheb Nayeri (Institutionen för kemi- och bioteknik, Teknisk ytkemi) ; M. T. Aronson ; Diana Bernin ; B. F. Chmelka ; Anna Martinelli (Institutionen för kemi- och bioteknik, Teknisk ytkemi)
Soft Matter (1744-683X). Vol. 10 (2014), 30, p. 5618-5627.
[Artikel, refereegranskad vetenskaplig]

We report on how the dynamical and structural properties of the ionic liquid 1-hexyl-3-methylimidazolium bis(trifluoromethanesulfonyl) imide (C(6)C(1)ImTFSI) change upon different degrees of confinement in silica gels. The apparent diffusion coefficients of the individual ions are measured by H-1 and F-19 pulsed field gradient nuclear magnetic resonance (PFG-NMR) spectroscopy, while the intermolecular interactions in the ionogels are elucidated by Raman spectroscopy. In addition, the local structure of the ionic liquid at the silica interface is probed by solid-state NMR spectroscopy. Importantly, we extend this study to a wider range of ionic liquid-to-silica molar ratios (x) than has been investigated previously, from very low (high degree of confinement) to very high (liquid-like gels) ionic liquid contents. Diffusion NMR measurements indicate that a solvation shell, with a significantly lower mobility than the bulk ionic liquid, forms at the silica interface. Additionally, the diffusion of the C(6)C(1)Im(+) and TFSI- ions decreases more rapidly below an observed molar ratio threshold (x < 1), with the intrinsic difference in the self-diffusion coefficient between the cation and anion becoming less pronounced. For ionic liquid molar ratio of x < 1, Raman spectroscopy reveals a different conformational equilibrium for the TFSI- anions compared to the bulk ionic liquid, with an increased population of the cisoid isomers with respect to the transoid. Concomitantly, at these high degrees of confinement the TFSI- anion experiences stronger ion-ion interactions as indicated by the evolution of the TFSI- characteristic vibrational mode at similar to 740 cm(-1). Furthermore, solid-state 2D Si-29{H-1} HETCOR NMR measurements establish the interactions of the ionic liquid species with the silica surface, where the presence of adsorbed water results in weaker interactions between Si-29 surface moieties and the hydrophobic alkyl protons of the cationic C(6)C(1)Im(+) molecules.

Nyckelord: PULSED-FIELD GRADIENT, X-RAY-SCATTERING, CONFORMATIONAL ISOMERISM, DIFFUSION-COEFFICIENT, MESOPOROUS SILICA, HYDROGEN SULFATE, ELECTROLYTES, NMR, TRANSPORT, IONOGELS, EJSKAL EO, 1965, JOURNAL OF CHEMICAL PHYSICS, V42, P288



Denna post skapades 2014-08-28.
CPL Pubid: 202091

 

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Institutioner (Chalmers)

Institutionen för kemi- och bioteknik, Teknisk ytkemi (2005-2014)
Svenskt NMR-centrum vid Göteborgs universitet (GU)

Ämnesområden

Yt- och kolloidkemi

Chalmers infrastruktur