Biopolymer-Grafted, Magnetically Tuned Halloysite Nanotubes as Efficient and Recyclable Spongelike Adsorbents for Anionic Azo Dye Removal.

Abstract

The quest for sustainable development and green chemistry had led to the design and synthesis of advanced adsorbent materials for efficient removal of pollutants in industrial effluents. Magnetic halloysite nanotubes with chitosan nanocomposite sponges were prepared by combining solution-mixing and freeze-drying. Magnetic@chitosan/halloysite (Fe3O4–HNT/CS) and spongelike chitosan/halloysite (HNT/CS) were used as adsorbents for the removal of Congo red dye in aqueous solution in a batch process. The as-prepared composites were characterized using scanning electron microscopy, energy-dispersive X-ray analysis, X-ray diffraction, vibrating-sample magnetometry, thermal gravimetry–differential scanning calorimetry, and Fourier transform infrared spectroscopy. Data from kinetic study were analyzed with pseudo-first-order and pseudo-second-order models, whereas the mechanism was analyzed using Bangham’s, Elovich’s, intraparticle, and double-exponential diffusion models. The equilibrium data were evaluated using Langmuir, Freundlich, Temkin, and Dubinin–Radushkevich isotherm models. The adsorption kinetics of dye removal followed the pseudo-first-order model with average rate constants of 0.260 and 0.196 min–1 for Fe3O4–HNT/CS and HNT/CS, respectively. The Langmuir adsorption isotherm best fitted the equilibrium data with R2 > 0.9 with maximum adsorption capacities of 41.54 and 54.49 mg g–1 obtained for HNT/CS and Fe3O4–HNT/CS, respectively. Negative values of ΔG° obtained from thermodynamic studies revealed that the adsorption process was spontaneous. The values of ΔH° and ΔS° obtained for Congo red dye removal were 69.46 and 39.54 kJ mol–1 and 240.5 and 145.1 J mol–1 K–1 for HNT/CS and Fe3O4–HNT/CS, respectively. The results indicated that CS–HNT is an excellent adsorbent; however, its magnetic modification further improved its recyclability and enhanced the performance for the removal of Congo red dye from aqueous solution.