Elucidating the Role of Diacid Anions in Governing Cellulose Dissolution and Microstructure of Regenerated Cellulose Aerogels

Tailoring solvent structures to regulate the dissolution and supramolecular assembly of cellulose is essential for developing advanced functional biobased materials. Herein, novel protic ionic liquids (PILs) composed of 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) and various diacid anions were systematically investigated for cellulose dissolution and regeneration. The malonate-based PIL (DBU-C3) demonstrated superior dissolution capacity (16.2 wt %) and low viscosity, attributed to an optimal balance between the electrostatic potential and steric accessibility of the anion. Furthermore, the diacid anion structure significantly influenced the morphological evolution of the regenerated cellulose materials. While DBU-C3 excelled in dissolution, the glutaric acid-based PIL (DBU-C5) proved ideal for fabricating aerogels with uniform nanofibrillar networks and high specific surface area (28.52 m 2 /g). This work elucidates the critical role of diacid anions in governing the solubility of cellulose and the microstructure of regenerated materials, offering a rational strategy for tailoring functional cellulose architectures.