Probing the evolutionary mechanism of the hydrogen bond network of cellulose nanofibrils using three DESs

Complex interactions between cellulose molecules and small molecules in Deep Eutectic Solvent (DES) systems can lead to dramatic changes in the structure of the hydrogen bond network in cellulose. However, the mechanism of interaction between cellulose and solvent molecules and the mechanism of evolution of hydrogen bond network are still unclear. In this study, cellulose nanofibrils (CNFs) were treated with DESs based on oxalic acid as hydrogen bond donors (HBD), and choline chloride, betaine, and N-methylmorpholine-N-oxide (NMMO) as hydrogen bond acceptors (HBA). The changes in the properties and microstructure of CNFs during treatment with the three types of solvents were investigated by Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD). The results showed that the crystal structures of CNFs were not changed during the process, but the hydrogen bond network evolved, increasing the crystallinity and crystallite size. Further analysis of the fitted peaks of FTIR and generalized two-dimensional correlation spectra (2DCOS) revealed that all three hydrogen bonds were disrupted to different degrees, the relative content changed, and evolved strictly in a certain order. These findings indicate that the evolution of hydrogen bond networks in nanocellulose has certain regularity.