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%. [Display omitted] •Covalent fabrication of chlorine-functionalized COF coating on stainless steel fiber for SPME.•The coating exhibited superior enrichment performance and fast extraction towards PCBs.•Multiple mechanisms involving π–π stacking interaction, hydrophobic and size-matching effect.•Sensitive and selective SPME-GC/MS method for ultra-trace analysis of PCBs in surface water.