Poly(ionic liquid)s threaded into covalent organic framework for synergistic capture of polybrominated diphenyl ethers

The efficient enrichment of trace polybrominated diphenyl ethers (PBDEs) in environmental waters remains challenging for environmental monitoring and analysis. Herein, a covalent organic frameworks-poly(ionic liquid)s hybrid material (COF-γ-PIL) is synthesized by threading poly(1-vinyl-3-methylimidazolium bis ((trifluoromethyl) sulfonyl) imide) into a vinyl-decorated COF via photopolymerization. The resultant hybrid retains the crystallinity and porosity of COF, thus offering adequate adsorption sites for the targets. PIL threaded in COF facilitates the synergistic capture of target molecules within the hybrid through multiple interactions, including Van der Waals forces, weak hydrogen bonding, and hydrophobic interactions. As a proof of concept, COF-γ-PIL was utilized as the fiber coating for SPME of PBDEs in waters prior to their analysis via GC-MS. Excellent analytical results were achieved, with wide linearity (0.01-100 ng L-1), low limits of detection (0.0021-0.014 ng L-1), and satisfactory recoveries (78.6%-103.6%). The outstanding extraction performance can be ascribed to the extraordinary flexibility of the active fraction on linear polymers threaded in COF, which facilitates collaborative capture for target molecules, as revealed by density functional theory (DFT) calculations. This work uncovers the microscopic mechanism for PBDEs capturing and provides new insights into the design of functionalized COF hybrids.