Cellulose dissolution in ionic liquid: ion binding revealed by neutron scattering

Vikram Singh Raghuwanshi, Yachin Cohen, Guillaume Garnier, Christopher J. Garvey, Robert A. Russell, Tamim Darwish, Gil Garnier

Research output: Contribution to journalArticleResearchpeer-review

Abstract

Dissolution of cellulose in 1-ethyl-3-methylimidazolium acetate (EMIMAc) ionic liquid (IL) was investigated by small-angle neutron scattering (SANS) with contrast variation. Cellulose and EMIMAc of different deuteration levels provide sufficient contrast in revealing the cellulose dissolution processes. Two experiments were performed: hydrogenated microcrystalline cellulose (MCC) was dissolved in deuterated IL (IL-D14), and deuterated bacterial cellulose (DBC) was dissolved in hydrogenated IL (IL-H14). Contrary to the expectation of high contrast between MCC and IL-D14, a dramatic reduction of the measured intensity (scattering cross section) was observed, about 1/3 of the value predicted based on the scattering length density (SLD) difference. This is attributed to the tight binding of acetate ions to the cellulose chains, which reduces the SLD difference. Measurements using small-angle X-ray scattering (SAXS) corroborate this effect by indicating increased contrast due to ion adsorption resulting in enhanced SLD difference. The experiments performed with DBC dissolution in IL-H14 suggest the presence of fractal aggregates of the dissolved cellulose, indicating lower solubility compared to the MCC. Contrast variation SANS measurements highlight tight ion binding of at least one acetate ion per anhydroglucose unit (AGU). EMIMAc is a successful cellulose solvent, as in addition to disrupting intermolecular hydrogen bonding, it imparts effective charge to the cellulose chains hindering their agglomeration in solution.

Original languageEnglish
Pages (from-to)7649-7655
Number of pages7
JournalMacromolecules
Volume51
Issue number19
DOIs
Publication statusPublished - 9 Oct 2018

Cite this

Raghuwanshi, Vikram Singh ; Cohen, Yachin ; Garnier, Guillaume ; Garvey, Christopher J. ; Russell, Robert A. ; Darwish, Tamim ; Garnier, Gil. / Cellulose dissolution in ionic liquid : ion binding revealed by neutron scattering. In: Macromolecules. 2018 ; Vol. 51, No. 19. pp. 7649-7655.
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abstract = "Dissolution of cellulose in 1-ethyl-3-methylimidazolium acetate (EMIMAc) ionic liquid (IL) was investigated by small-angle neutron scattering (SANS) with contrast variation. Cellulose and EMIMAc of different deuteration levels provide sufficient contrast in revealing the cellulose dissolution processes. Two experiments were performed: hydrogenated microcrystalline cellulose (MCC) was dissolved in deuterated IL (IL-D14), and deuterated bacterial cellulose (DBC) was dissolved in hydrogenated IL (IL-H14). Contrary to the expectation of high contrast between MCC and IL-D14, a dramatic reduction of the measured intensity (scattering cross section) was observed, about 1/3 of the value predicted based on the scattering length density (SLD) difference. This is attributed to the tight binding of acetate ions to the cellulose chains, which reduces the SLD difference. Measurements using small-angle X-ray scattering (SAXS) corroborate this effect by indicating increased contrast due to ion adsorption resulting in enhanced SLD difference. The experiments performed with DBC dissolution in IL-H14 suggest the presence of fractal aggregates of the dissolved cellulose, indicating lower solubility compared to the MCC. Contrast variation SANS measurements highlight tight ion binding of at least one acetate ion per anhydroglucose unit (AGU). EMIMAc is a successful cellulose solvent, as in addition to disrupting intermolecular hydrogen bonding, it imparts effective charge to the cellulose chains hindering their agglomeration in solution.",
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Cellulose dissolution in ionic liquid : ion binding revealed by neutron scattering. / Raghuwanshi, Vikram Singh; Cohen, Yachin; Garnier, Guillaume; Garvey, Christopher J.; Russell, Robert A.; Darwish, Tamim; Garnier, Gil.

In: Macromolecules, Vol. 51, No. 19, 09.10.2018, p. 7649-7655.

Research output: Contribution to journalArticleResearchpeer-review

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