Efficient extraction of carboxylated nanocellulose from ionoSolv pulps with alkaline H2O2 assisted oxidation

We report a simple procedure to produce carboxylated cellulose nanocrystals (CNCs) from grassy biomass (Miscanthus X Giganteus) using a two-step approach consisting of biomass fractionation with a protic ionic liquid followed by oxidation of the resulting cellulose-rich pulps with H₂O₂. The impact of the fractionation severity on the composition, structure, size, thermal stability, crystallinity, and degree of polymerization of the CNCs was evaluated. It was found that fractionation severity had a large impact on the pulp purity and its reactivity during the oxidation stage. Nevertheless, the impact on the properties of the final CNCs was small. CNCs were recovered as suspensions of negatively charged, electrostatically stable, needle-like CNCs with a lower degree of crystallinity (58–61%) compared to the precursor pulps (65–69%). The presence of carboxyl groups on the surface of the CNCs facilitated the stability of the suspensions but also caused a slight decrease in the thermal stability of the CNCs. A milder oxidation process followed by ultrasonication allowed us to maximize the production of CNCs while better preserving the degree of crystallinity of the cellulose (63%).