Hydrophobization of aerogels based on chitosan, nanocellulose and tannic acid: Improvements on the aerogel features and the adsorption of contaminants in water

Hydrophobic chitosan aerogels are promising adsorbents for immiscible contaminants such as oils and organic solvents. However, few studies have reported the application of hydrophobic aerogels as adsorbent for organic contaminants dissolved in water. Herein, novel highly hydrophobic chitosan (CS) beads containing cellulose nanocrystals (CNC) and hydrophobized tannic acid (HTA) composite were prepared with different CS and CNC-HTA content to achieve an optimized adsorbent to remove emerging contaminants from water in batch and fixed-bed assays. The CS@CNC-HTA beads properties were assessed by FTIR, XRD, SEM, XPS, Micro-CT, WCA, and zeta potential. Supramolecular interactions and physical interlacements between CS and CNC-HTA enabled the formation of CS@CNC-HTA beads with high porosity (98.6%), great volume of open pore space (10.16 mm3) and hydrophobicity (121.8°). The 1:1 CS@CNC-HTA beads showed the best performance for removing the pharmaceutical sildenafil citrate, the basic blue 26 dye, and the surfactant cetylpyridinium chloride, reaching adsorption capacities of 86 (73%), 375 (84%), and 390 (90%) mg.g-1, respectively. The 1:1 CS@CNC-HTA beads efficiently removed sildenafil citrate, basic blue 26 and cetylpyridinium chloride in fixed-bed experiments with exhaustion times of 890, 300, and 470 min, respectively. Theoretical calculations and adsorption assays indicate that the main attractive interactions are pyridinium-π, π-π, electrostatic and hydrophobic.