In-situ fabrication of a chlorine-functionalized covalent organic framework coating for solid-phase microextraction of polychlorinated biphenyls in surface water

The functionalization of covalent organic frameworks (COFs) identifies significant potential for developing selective coating materials for solid-phase microextraction (SPME). Herein, a chlorine-functionalized covalent organic framework (CF-COF) was in-situ synthesized by employing triformylphloroglucinol (Tp) and 2,5-dichloro-1,4-phenylenediamine (2,5-DCA) as monomers on an amino-functionalized stainless steel wire. The obtained CF-COF coated fiber exhibited a higher enrichment capacity for polychlorinated biphenyls (PCBs) than commercial fibers and non-chlorinated COF fiber, owing to a more hydrophobic surface, size-matching effect, a large number of micropores and the π-π stacking interactions between COF coating and analytes. As a practical application, the CF-COF coated fiber was applied to the headspace extraction of 17 PCBs prior to their quantification by GC/MS. The established analytical method offered a good linearity in the range of 0.1-1000 ng L-1, low detection limits of 0.0015-0.0088 ng L-1, and satisfactory enhancement factors (EFs) of 699-4281. The repeatability for single fiber and the fiber-to-fiber reproducibility was lower than 9.26% and 9.33%, respectively. The proposed method was verified to be sensitive, selective, and applicable for the analysis of ultra-trace PCBs in environmental surface water samples with the recoveries ranged from 78.7% to 124.0%.