Ultrasonic preparation of fluorinated functionalised magnetic covalent organic frameworks for adsorption and removal of tetrabromobisphenol A

Abstract

Tetrabromobisphenol A (TBBPA) was a widely used brominated flame retardant, and had attracted widespread attention from researchers due to its potential adverse effects on ecosystems and human health. Therefore, to eliminate the negative effects of TBBPA, methods for the adsorption and removal of TBBPA are urgently needed. In this work, the fluorine-functionalised magnetic covalent organic frameworks (Fe3O4@TFAPT-TFPA@COF) were first prepared through a simple and rapid ultrasound method to efficiently adsorpt and remove TBBPA. Firstly, a pre-modification strategy was used to modify fluorine functional groups onto amine monomers via superacid catalyzed trimerization. Then, amine and aldehyde monomers undergo Schiff base reaction smoothly to form a COF layer coated on the surface of Fe3O4 nanoparticles. The characterisation results indicated that the prepared Fe3O4@TFAPT-TFPA@COF had a high surface area, porosity, crystallinity and abundant F-containing binding sites. Additionally, the adsorption process of prepared Fe3O4@TFAPT-TFPA@COF complied with pseudo-second-order kinetics and the Langmuir adsorption model. It had a large adsorption capacity (107.5 mg g−1), could effectively remove tetrabromobisphenol A within 4 minutes and had excellent regeneration ability within eighth repetitions. Finally, tetrabromobisphenol A was efficiently removed by a small separation column loaded with Fe3O4@TFAPT-TFPA@COF, achieving levels below the detection limit (< 0.05 mg L−1) and providing practical application value for the real-time removal of TBBPA. The main mechanisms promoting the excellent adsorption performance of TBBPA were through halogen bonds, electrostatic interactions, π-π stacking, and hydrogen bonding interactions, providing potential reference value for the adsorption ability and mechanism of TBBPA in other applications.