Cellulose nanomaterials, such as cellulose nanocrystals (CNCs), have received enormous attention in various material research fields due to their unique properties and green/sustainable nature, among other qualities. Herein, we report hollow-type annular cellulose nanocrystals (HTA-CNCs), which are generated by following a high-intensity ultrasonic treatment. The advanced aberration-corrected transmission electron microscopy results reveal that HTA-CNCs exhibit ring structures with a typical diameter of 10.0-30.0 nm, a width of 3.0-4.0 nm, and a thickness of 2.0-5.0 nm, similar to those of elementary crystallites. The X-ray diffraction measurements show that the as-prepared HTA-CNCs maintain the cellulose I structure. The changes in structure and hydrogen-bonding characteristics of HTA-CNCs are further determined based on the FT-IR results after deconvolution fitting, showing that three types of hydrogen bonds decrease and the content of free OH increases in HTA-CNCs compared with those in the original CNCs. Furthermore, molecular dynamics simulation is carried out to support the experimental study. The formation of HTA-CNCs might be attributed to the structural change and entropy increase. The hollow-type annular CNCs may have broad value-added applications as cellulose nanomaterials in different fields.
Keywords: cellulose nanocrystals; high-intensity ultrasonic treatment; hollow structure; hollow-type annular CNCs; spherical aberration-corrected transmission electron microscopy.