In situ preparation of MOF-199 into the carrageenan-grafted-polyacrylamide@Fe3O4 matrix for enhanced adsorption of levofloxacin and cefixime antibiotics from water

• Published in: Environmental research Vol. 233; p. 116466
• Main Authors: Salehi, Mohammad Mehdi, Hassanzadeh-Afruzi, Fereshte, Heidari, Golnaz, Maleki, Ali, Nazarzadeh Zare, Ehsan
• Format: Journal Article
• Language: English
• Published: Elsevier Inc 15.09.2023
• Subjects: Carrageenan; Cefixime; Hydrogel magnetic nanocomposite; Levofloxacin; MOF-199; Pharmaceutical wastewater treatment; Levofloxacin; BJH; APS; Ms; NaOH; Hydrogel magnetic nanocomposite; XRD; MBA; EWC; CFX; MOF-199; FTIR; PAAm; EDX; Cefixime; DMF; Cu (NO3)2·3H2O; MNPs; FeCl3·6H2O; FESEM; H3BTC; MOFs; Pharmaceutical wastewater treatment; d.w; Wd; TGA; BET; Fe3O4; HCL; 3D; VSM; kC; Carrageenan; LEV; FeCl2·4H2O; Ws
• ISSN: 0013-9351; 1096-0953
• DOI: 10.1016/j.envres.2023.116466

In this research study, a novel method, an in-situ growth approach, to incorporate metal-organic framework (MOF) into carrageenan-grafted- polyacrylamide-Fe3O4 substrate was introduced. Carrageenan-grafted-polyacrylamide-Fe3O4/MOF nanocomposite (kC-g-PAAm@Fe3O4-MOF-199) was fabricated utilizing three stages. In this way, the polyacrylamide (PAAm) was grafted onto the carrageenan (kC) backbone via free radical polymerization in the presence of methylene bisacrylamide (MBA) as cross-linker and Fe3O4 magnetic nanoparticles. Next, the kC-g-PAAm@Fe3O4 was modified by MOF-199 via an in-situ solvothermal approach. Several analyses such as Fourier transform infrared spectroscopy (FT-IR), X-Ray diffraction (XRD), field emission scanning electron microscopy (FESEM), energy-Dispersive X-ray Spectroscopy (EDX), thermogravimetric analysis (TGA), vibrating sample magnetometer (VSM), Brunauer-Emmett-Teller (BET) demonstrated the successful synthesis of kC-g-PAAm@Fe3O4-MOF-199 magnetic hydrogel nanocomposite. The XRD pattern of magnetic hydrogel nanocomposite illustrated characteristic peaks of Fe3O4, neat kC, and MOF-199 with enhanced crystallinity in comparison with kC-g-PAAm@Fe3O4. TGA showed it has a char yield of 24 wt% at 800 °C. VSM confirmed its superparamagnetic behavior (with Ms of 8.04 emu g−1), and the BET surface area of kC-g-PAAm@Fe3O4-MOF-199 was measured at 64.864 m2 g−1, which was higher than that of kC-g-PAAm@Fe3O4 due to the highly porous MOF-199 incorporation with a BET surface area of 905.12 m2 g−1). The adsorption effectiveness of kC-g-PAAm@Fe3O4-MOF-199 for eliminating cephalosporin and quinolones antibiotics, i.e., Cefixime (CFX) and Levofloxacin (LEV) from the aquatic area was considered. Several experimental setups were used to evaluate the efficacy of adsorption, such as solution pH, amount of adsorbent, contact duration, and initial concentration. The maximum adsorption capacity (Qmax) of the prepared magnetic hydrogel nanocomposite was found to be 2000 and 1666.667 mg−1 for LEV and CFX using employing 0.0025 g of adsorbent. The Freundlich isotherm model well described the experimental adsorption data with R2CFX = 0.9986, and R2LEV = 0.9939. And the adsorption kinetic data were successfully represented by the pseudo-second-order model with R2LEV = 0.9949 and R2CFX = 0.9906. Hydrogen bonding, π-π interaction, diffusion, and entrapment in the hydrogel network all contributed to the successful adsorption of both antibiotics onto the kC-g-PAAm@Fe3O4-MOF-199 adsorbent. Other notable physicochemical properties include the three-dimensional structure and availability of the reactive adsorption sites. Moreover, the adsorption/desorption efficacy of magnetic hydrogel nanocomposites was not significantly diminished after four cycles of recovery. [Display omitted] •A MOF-199 was prepared via in situ method onto carrageenan-grafted polyacrylamide hydrogel.•High adsorption capacity (2000 and 1666.667 mg/g) of LEV and CFX was achieved.•Adsorption data were fitted by Freundlich isotherms and pseudo second-order kinetics.•The kC-g-PAAm@Fe3O4-MOF-199 nanoadsorbent reused at least four times.