In situ hydrothermal growth of a dual-ligand metal–organic framework film on a stainless steel fiber for solid-phase microextraction of polycyclic aromatic hydrocarbons in environmental water samples

Abstract

Effective enrichment and determination of polycyclic aromatic hydrocarbons (PAHs) in environmental aqueous solutions is still a major challenge because of their poor solubility and low concentration in the environmental matrix. Solid-phase microextraction (SPME) has been proven to be an effective technique for analyzing trace analytes from environmental samples. Herein, we report the fabrication of a dual-ligand metal–organic framework (MOF) bio-MOF-1-coated stainless steel fiber via an in situ growth approach for SPME of six PAHs in water samples. Such MOF-based SPME in combination with gas chromatography (GC) gave enhancement factors of 3104–5980, ranges of 10–100 μg L⁻¹ for Nap, Ace, and Fle, 2.5–100 μg L⁻¹ for Phen, 0.1–100 μg L⁻¹ for FluA and Pyr, detection limits (S/N = 3) of 0.02–5.57 μg L⁻¹, and quantitation limits (S/N = 10) of 0.14–17.2 μg L⁻¹ for the studied PAHs. The recoveries obtained by spiking 10 μg L⁻¹ PAHs in water samples ranged from 80% to 115%. The results showed that π–π interaction with biphenyldicarboxylate and π-complexation between aromatic rings and the pyrimidine in the pores of bio-MOF-1 play significant roles in the extraction of PAHs.