Cellulose Dissolution in Ionic Liquid: Ion Binding Revealed by Neutron Scattering

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.