A water resistant solid-phase microextraction fiber with high selectivity prepared by a metal organic framework with perfluorinated pores

•Zn-FMOF@PI SPME fiber exhibited rare highly selective extraction for benzene.•Zn-FMOF@PI SPME fiber exhibited highly hydrophobic character.•Zn-FMOF@PI afforded good stabilities due to the auxiliary material PI.

A novel solid-phase microextraction (SPME) fiber was fabricated by the construction of fluorous metal organic frameworks (FMOF) and a polyimide (PI) composite strategy. As an auxiliary material, PI was expected to help FMOF particles form well-knit film on the surface of stainless steel wire and reinforce the coating, and FMOF was expected to afford a special structure to absorb, extract and enrich. Furthermore, it was explored for the headspace SPME (HS-SPME) of six volatile aromatic compounds (VACs) from water samples followed by gas chromatographic (GC) separation with flame ionization detection. Under the optimized conditions, the fiber afforded wide linear ranges (1–1000 μg L−1), low detection limits (0.15–0.9 μg L−1) and acceptable repeatability (<4.6%) and reproducibility (<7.3%). The FMOF@PI coated fiber not only offered large enhancement factors for benzene (1227) but also exhibited high extraction selectivity for benzene to other benzene homologues, hydrocarbons and phenols; for example, the extraction ratio of benzene to toluene, n-hexane and phenol could be as high as 10.2, 64.1 and 32.3, respectively. Moreover, the FMOF@PI-coated fiber afforded good thermal, water and organic solvent stabilities, and a long lifetime (over 200 times). The developed method was successfully applied to the determination of VACs in wastewater samples.