Lightweight cellulose II aerogels featuring densities of about 40–70 mg cm−3 were prepared from 1 to 3% solutions of different pulps in hot (60°C) tetra-n-butylammonium fluoride (TBAF)·H2O/dimethyl sulfoxide (DMSO) by (i) the coagulation of cellulose with EtOH to afford self-standing, transparent and homogeneous gels, (ii) gel ripening and washing, (iii) solvent exchange and (iv) supercritical carbon dioxide (scCO2) drying. Size exclusion chromatography (SEC) analyses confirmed that the chemical integrity of cellulose is largely preserved at short dissolution times. Dissolution of more than 2% of cellulose at a sufficiently low viscosity for solution, casting was achieved after the water content of TBAF was reduced to a value equaling that of the monohydrate. Intriguingly, the obtained aerogels featured higher specific surfaces (≤470 m2 g−1) than comparable materials prepared from other cellulose solvents. This is due to the particular morphology of TBAF aerogels, which is supposedly formed by spinodal decomposition of the cellulose/solvent mixture upon exposure to the cellulose antisolvent. As a result, largely homogeneous three-dimensional (3D) networks of agglomerated cellulose spheres were formed, which simultaneously acted as supporting scaffolds for interconnected micron-size voids. As cellulose spheres are composed of very small interwoven nanofibers, TBAF-derived aerogels contain a high portion of micropores and small amounts of mesopores, too.

Biopolymer aerogels of appropriate open-porous morphology, nanotopology, surface chemistry, and mechanical properties can be promising cell scaffolding materials. Here, we report a facile approach towards the preparation of cellulose phosphate aerogels from two types of cellulosic source materials. Since high degrees of phosphorylation would afford water-soluble products inappropriate for cell scaffolding, products of low DS P (ca. 0.2) were prepared by a heterogeneous approach. Aiming at both i) full preservation of chemical integrity of cellulose during dissolution and ii) utilization of specific phase separation mechanisms upon coagulation of cellulose, TBAF·H 2 O/DMSO was employed as a non-derivatizing solvent. Sequential dissolution of cellulose phosphates, casting, coagulation, solvent exchange, and scCO 2 drying afforded lightweight, nano-porous aerogels. Compared to their non-derivatized counterparts, cellulose phosphate aerogels are less sensitive towards shrinking during solvent exchange. This is presumably due to electrostatic repulsion and translates into faster scCO 2 drying. The low DS P values have no negative impact on pore size distribution, specific surface (S BET ≤ 310 m 2 g −1 ), porosity (Π 95.5-97 vol.%), or stiffness (Eρ ≤ 211 MPa cm 3 g −1 ). Considering the sterilization capabilities of scCO 2 , existing templating opportunities to afford dual-porous scaffolds and the good hemocompatibility of phosphorylated cellulose, TBAF·H 2 O/DMSO can be regarded a promising solvent system for the manufacture of cell scaffolding materials.