Efficient removal of tetracycline by a hierarchically porous ZIF-8 metal organic framework

Abstract

Most reported metal organic frameworks (MOFs) have microporous structures and defective active sites, limiting their practical application to macromolecular substances. A hierarchical porous zeolitic imidazolate framework-8 (ZIF-8) was prepared using poly(diallyldimethylammonium chloride) (PDDA) as a structure-directing agent under facile “aqueous room-temperature” conditions to increase the mass transfer and adsorption capacity tetracycline hydrochloride (TCH). The ZIF-8 pore structure and morphology were synchronously tuned by controlling the PDDA molecular weight and dosage. Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), Bruner-Emmett-Teller (BET), scanning electron microscopy (SEM), NH3-temperature-programmed desorption (NH3-TPD) and adsorption results revealed abundant pore structures and open metal sites in the prepared materials, along with excellent TCH adsorption performance compared with ZIF-8, despite decreased BET surface areas. Initial screens revealed large adsorption capacities of hierarchical porous ZIF-8P3(4) (976.8 mg g−1) due to the presence of more abundant unsaturated metal sites than ZIF-8 and novel hierarchical porous structures. Therefore, TCH adsorption on ZIF-8 and ZIF-8P3(4), including the kinetics, isotherms, thermodynamics and pH effect, was studied. The adsorption process follows pseudo-second-order kinetics and the Freundlich models better, indicating multilayer adsorption of TCH on the surface of the two absorbents. Adsorption behavior test, FTIR, XPS, BET and XRD results show that TCH adsorption on ZIF-8 and ZIF-8P3(4) most likely involves coordination bonds, electrostatic and π-π interactions, hydrogen bonds, and pore-filling effects. This study provides new insights into the template preparation of MOFs with high adsorption performance as potentially economical adsorbents to remove organic matter from contaminated water.