Difunctional covalent organic framework hybrid material for synergistic adsorption and selective removal of fluoroquinolone antibiotics

Abstract

Due to the low efficiency of traditional sewage treatment methods, the effective removal of zwitterionic fluoroquinolone (FQs) antibiotics is of vital significant for environment protection. In this work, a SO3H-anchored covalent organic framework (TpPa-SO3H) was deliberately designed by linking phenolic trialdehyde with triamine through Schiff reaction, then low-content Tb3+ ions were loaded onto covalent organic framework according to wet-chemistry immersion dispersion method which benefitting for efficient FQs antibiotics uptaking. Tb@TpPa-SO3H functionalized with regularly distributed sulfonic acid groups and terbium ions which could provide difunctional binding sites. Tb3+ sites could capture carboxylic acid group of FQs molecules according to the complexes coordination effect and sulfonic acid sites play a significant role in the adsorption of FQs molecules through electrostatic interaction with amine group. Tb@TpPa-SO3H with dual complementary function sites exhibited ultra-fast adsorption kinetics (< 2min, average over 99% removing rate) and high adsorption capacities of 989, 956, and 998mgg-1 for Norfloxacin (NOR), ciprofloxacin (CIP), enrofloxacin (ENR), respectively. Furthermore, Tb@TpPa-SO3H showed excellent selectivity for the adsorption of FQs in tanglesome system. This work not only explored synergistic adsorption in ion-functionalized 2D covalent organic framework with dual binding sites, but also delineated a promising strategy for the elimination of organic pollutants in environmental remediation.