A water resistance magnetic graphene-anchored zeolitic imidazolate framework for efficient adsorption and removal of residual tetracyclines in wastewater.

Water-resistant magnetic graphene-anchored zeolite imidazolate (Fe3O4/ZIF-8-G) composite materials with the largest surface area are formed by directly growing a hydrophobic ZIF-8 skeleton onto a graphene support through self-assembly in methanol. Fe3O4/ZIF-8-G hybrid composite has water resistance and super strong adsorption capacity, and is used as an effective adsorbent for adsorption and removal of residual tetracycline in wastewater. The morphologies and structure, as well as water resistance of Fe3O4/ZIF-8-G, were characterized using Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetry analysis (TGA), N2 adsorption and pHPZC. The adsorption for tetracycline (TC), oxytetracycline (OTC) and chlortetracycline (CTC) followed pseudo-second-order kinetics and fitted the Freundlich adsorption model with the simultaneous adsorption capacity for TC (382.58 mg g-1), OTC (565.94 mg g-1) and CTC (608.06 mg g-1) at pH 5-6 for 10 h. These were much higher than previously reported results for the removal of tetracycline from aqueous solutions. The used Fe3O4/ZIF-8-G could be effectively reused and recycled at least five times without significant loss of adsorption capacity. The hydrophobic and π-π interaction between the aromatic rings of TCs and the aromatic imidazole rings of the ZIF-8-G framework were the main adsorption mechanism on the surface of Fe3O4/ZIF-8-G. Constructing a hydrophobic surface of ZIF-8/G framework resulted in a reduction of the hydrophilic sites of the surface. This can improve stability and selective adsorption of ZIF-8-G framework. In addition, the results show no significant difference in the adsorption kinetics and adsorption capacity of Fe3O4/ZIF-8-G for TC, OTC and CTC in pure water and wastewater.