Methionine-Functionalized Graphene Oxide/Sodium Alginate Bio-Polymer Nanocomposite Hydrogel Beads: Synthesis, Isotherm and Kinetic Studies for an Adsorptive Removal of Fluoroquinolone Antibiotics.

In spite of the growing demand for new antibiotics, in the recent years, the occurrence of fluoroquinolone antibiotics (as a curative agent for urinary tract disorders and respiratory problems) in wastewater have drawn immense attention. Traces of antibiotic left-overs are present in the water system, causing noxious impact on human health and ecological environments, being a global concern. Our present work aims at tackling the major challenge of toxicity caused by antibiotics. This study deals with the efficient adsorption of two commonly used fluoroquinolone (FQ) antibiotics, i.e., Ofloxacin (OFX) and Moxifloxacin (MOX) on spherical hydrogel beads generated from methionine‒functionalized graphene oxide/ sodium alginate polymer (abbreviated Met-GO/SA) from aqueous solutions. The composition, morphology and crystal phase of prepared adsorbents were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), Fourier transform infrared spectroscopy (FTIR), high-resolution transmission electron microscopy (HR-TEM) and thermogravimetric analysis/differential thermogravimetry (TGA/DTG). Batch adsorption tests are followed to optimize the conditions required for adsorption process. Both functionalized and non-functionalized adsorbents were compared to understand the influence of several experimental parameters, such as, the solution pH, contact time, adsorbent dosage, temperature and initial concentration of OFX and MOX on adsorption. The obtained results indicated that the functionalized adsorbent (Met-GO/SA) showed a better adsorption efficiency when compared to non-functionalized (GO/SA) adsorbent. Further, the Langmuir isotherm was validated as the best fitting model to describe adsorption equilibrium and pseudo second-order-kinetic model fitted well for both types of adsorbate. The maximum adsorption capacities of Met-GO/SA were 4.11 mg/g for MOX and 3.43 mg/g for OFX. Thermodynamic parameters, i.e., ∆G°, ∆H° and ∆S° were also calculated. It was shown that the overall adsorption process was thermodynamically favorable, spontaneous and exothermic in nature. The adsorbents were successfully regenerated up to four cycles with 0.005 M NaCl solutions. Overall, our work showed that the novel Met-GO/SA nanocomposite could better contribute to the removal of MOX and OFX from the liquid media. The gel beads prepared have adequate features, such as simple handling, eco-friendliness and easy recovery. Hence, polymer gel beads are promising candidates as adsorbents for large-scale water remediation.

Adsorption of cationic dyes, drugs and metal from aqueous solutions using a polymer composite of magnetic/ß-cyclodextrin/activated charcoal/Na alginate: Isotherm, kinetics and regeneration studies.

In this work, we successfully synthesized novel polymer gel beads based on functionalized iron oxide (Fe3O4), activated charcoal (AC) particles with ß-cyclodextrin (CD) and sodium alginate (SA) polymer (Fe3O4/CD/AC/SA), by a simple, reproducible and inexpensive method. These beads proved to be versatile and strong adsorbents with magnetic properties and high adsorption capacity. The composites were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, energy dispersive X-ray spectroscopy, vibrating sample magnetometry, adsorption at -196 °C, high resolution transmission electron microscopy, thermogravimetric analysis and point of zero charge measurements. Two dyes, two drugs and one metal were used to test the adsorption capability of the prepared polymer nanocomposite. The adsorbent showed good removal efficiencies for the studied pollutants, especially the cationic dyes and the metal, when compared to other low-cost adsorbents. The saturated adsorption capacity of Fe3O4/CD/AC/SA reached 5.882 mg g-1 for methyl violet (MV), 2.283 mg g-1 for brilliant green (BG), 2.551 mg g-1 for norfloxacin (NOX), 3.125 mg g-1 for ciprofloxacin (CPX), 10.10 mg g-1 for copper metal ion (Cu(II)). The adsorption isotherm studies showed that data fitted well with Langmuir and Temkin isotherms models. The kinetic data showed good correlation coefficient with low error function for the pseudo-second order kinetic model. The data analysis was carried out using error and regression coefficient functions for the estimation of best-fitting isotherm and kinetic models, namely: chi-square test (χ2) and sum of the squares of errors (SSE). The activation energy was found to be 47.68 kJ mol-1 for BG, 29.09 kJ mol-1 for MV, 28.93 kJ mol-1 for NOX, 4.53 kJ mol-1 for CPX and 17.08 kJ mol-1 for Cu(II), which represent chemisorption and physisorption behavior of sorbent molecules. The polymer composites can be regenerated and easily separated from aqueous solution without any weight loss. After regeneration, the Fe3O4/CD/AC/SA beads still have good adsorption capacities up to four cycles of desorption and adsorption. The results indicate that the polymer gel beads are promising adsorbents for the removal of different categories of toxicants (like dyes, drugs and metal) in single adsorbate aqueous systems. Thus, the novel Fe3O4/CD/AC/SA beads can be effectively employed for a large-scale applications as environmentally compatible materials for the adsorption of different categories of pollutants.