Impact of the Configurational Microstructure of Carboxylate-Rich Chitosan Beads on Its Adsorptive Removal of Diclofenac Potassium from Contaminated Water

A novel adsorbent–contaminant system was investigated for its ability to remove a contaminant of emerging concern, diclofenac potassium, from contaminated water. Bio-based crosslinked chitosan beads functionalized with poly(itaconic acid) side chains were examined for their potential to remove the emerging contaminant. To evaluate the impact of the polymeric microstructure on its adsorptive capacity, several adsorbent samples were prepared using different combinations of initiator and monomeric concentrations. Fourier Transform Infrared (FTIR) analysis confirmed the crosslinking of the chitosan chains and the incorporation of the carboxylic groups on the surface of the final chitosan beads. After the grafting copolymerization process, an additional peak at 1726 cm−1 corresponding to the carboxylic C=O groups of the grafted chains appeared, indicating the successful preparation of poly(IA)-g-chitosan. Thermal stability studies showed that the grafting copolymerization improved the thermal stability of the beads. X-ray and Scanning Electron Microscopy confirmed the successful grafting of the itaconic acid on the surface of the beads. The study revealed that the higher the initiator concentration, the greater the number of side chains, whereas the higher the monomeric concentration, the longer the length of these side chains. The adsorption mechanism involved hydrogen bonding to the carboxylic groups of the grafted chains along with n-π* stacking interaction between the amino group of the chitosan and the aromatic rings of diclofenac potassium. The adsorption efficiencies of diclofenac potassium onto the grafted beads were significantly improved compared to the unfunctionalized chitosan beads, reaching values above 90%. The removal efficiency of grafted chitosan increased with an increase in the concentration in the range of 10–30 ppm and then flattened out in the range of 30–50 ppm. The removal efficiencies of 1–50 ppm of DCF ranged between about 75% and 92% for the grafted chitosan and 30–45% for the crosslinked chitosan. Rapid adsorption occurred within 20 min for all grafted sample combinations, and the adsorption kinetics followed a pseudo-second-order model with qe values ranging from 28 to 44.25 g/mg and R2 values greater than 0.9915. The results highlight the potential of grafted chitosan beads in removing emerging contaminants from contaminated water without harming the environment.