Piperazine-linked metal covalent organic framework-coated fibers for efficient electro-enhanced solid-phase microextraction of chlorophenols

Conductive covalent organic frameworks (COFs) have received considerable attention and are critical in various applications such as electro-enhanced solid-phase microextraction (EE-SPME). In this work, a novel piperazine-linked copper-doped phthalocyanine metal covalent organic framework (CuPc-MCOF) was synthesized with good stability and high electrical conductivity. The synthesized CuPc-MCOF was then used as an EE-SPME coating material for extraction of five trace chlorophenols (CPs), including 2,4-dichlorophenol (2,4-DCP), 2,6-dichlorophenol (2,6-DCP), 2,4,6-trichlorophenol (2,4,6-TCP), 2,4,5-trichlorophenol (2,4,5-TCP) and 2,4,5,6-tetrachlorophenol (2,4,5,6-TCP), exhibiting excellent extraction performance because of various synergistic forces between CuPc-MCOF fibers and CPs. By combining EE-SPME with gas chromatography-tandem mass spectrometry (GC–MS/MS), a sensitive method for CPs detection was established with a low limit of detection (0.8–5 ng L⁻¹) and good reproducibility (RSD≤8.4%, n = 3). This method was then successfully applied to the analysis of trace CPs in real samples of seawater and seafood. Results showed that the developed CuPc-MCOF coating material possessed superior extraction performance and potential application in extraction of trace polar pollutants from complex samples.