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The impact of selected cellulose solvent systems based on the principal constituents tetrabutylammonium fluoride (TBAF), 1-ethyl-3-methyl-1 H -imidazolium-acetate, N -methylmorpholine- N -oxide, or calcium thiocyanate octahydrate (CTO) on the properties of cellulose II aerogels prepared from these solvent systems has been investigated as a means towards tailoring cellulose aerogel properties with respect to specific applications. Cotton linters were used as representative plant cellulose. Cellulose was coagulated from solutions with comparable cellulose content, and dried with supercritical carbon dioxide after solvent exchange. The resulting bulk aerogels were comprehensively morphologically and mechanically tested to relate structure and mechanical properties. Different solvent systems caused considerable differences in the properties of the bulk samples, such as internal surface area (nitrogen sorption), morphology, porosity (He pycnometry, thermoporosimetry), and mechanical stability (compression testing). The results of SAXS, WAXS, and solid-state 13 C NMR spectroscopy suggest that this is due to different mechanisms of cellulose self-assembling on the supramolecular and nanostructural level, respectively, as reflected by the broad ranges of cellulose crystallinity, fibril diameter, fractal dimension and skeletal density. Both solid state NMR and WAXS experiments confirmed the sole existence of the cellulose II allomorph for all aerogels, with crystallinity reaching a maximum of 46-50 % for CTO-derived aerogels. Generally, higher fibril diameter, degree of crystallinity, hence increased skeletal density were associated with good preservation of shape and dimension throughout conversion of lyogels to aerogels, and enhanced mechanical stability, but somewhat reduced specific surface area. Amorphous, yet highly rigid aerogels derived from TBAF/DMSO mixtures deviated from this trend, most likely due to their particular homogeneous and nanostructured morphology.

Photoluminiscent (PL) cellulose aerogels of variable shape containing homogeneously dispersed and surface-immobilized alloyed (ZnS) x (CuInS 2 ) 1-x /ZnS (core/shell) quantum dots (QD) have been obtained by (1) dissolution of hardwood prehydrolysis kraft pulp in the ionic liquid 1-hexyl-3-methyl-1 H -imidazolium chloride, (2) addition of a homogenous dispersion of quantum dots in the same solvent, (3) molding, (4) coagulation of cellulose using ethanol as antisolvent, and (5) scCO 2 drying of the resulting composite aerogels. Both compatibilization with the cellulose solvent and covalent attachment of the quantum dots onto the cellulose surface was achieved through replacement of 1-mercaptododecyl ligands typically used in synthesis of (ZnS) x (CuInS 2 ) 1-x /ZnS (core-shell) QDs by 1-mercapto-3-(trimethoxysilyl)-propyl ligands. The obtained cellulose-quantum dot hybrid aerogels have apparent densities of 37.9-57.2 mg cm -3 . Their BET surface areas range from 296 to 686 m 2 g -1 comparable with non-luminiscent cellulose aerogels obtained via the NMMO, TBAF/DMSO or Ca(SCN) 2 route. Depending mainly on the ratio of QD core constituents and to a minor extent on the cellulose/QD ratio, the emission wavelength of the novel aerogels can be controlled within a wide range of the visible light spectrum. Whereas higher QD contents lead to bathochromic PL shifts, hypsochromism is observed when increasing the amount of cellulose at constant QD content. Reinforcement of the cellulose aerogels and hence significantly reduced shrinkage during scCO 2 drying is a beneficial side effect when using α-mercapto-ω-(trialkoxysilyl) alkyl ligands for QD capping and covalent QD immobilization onto the cellulose surface.