Ketoenamine Covalent Organic Framework Coating for Efficient Solid-Phase Microextraction of Trace Organochlorine Pesticides

Fiber coating is a key part of solid-phase microextraction (SPME) technology, and it determines the selectivity, sensitivity, and reproducibility of the analytical method. A ketoenamine covalent organic framework called Tp–Azo–COF with rich electronegative N atoms was prepared as an SPME coating in this work. The Tp–Azo–COF coating had a large surface area of 1218 m2 g–1 and good thermal and chemical stability, and it was applied for the extraction of organochlorine pesticides (OCPs). According to quantum chemistry calculations, the adsorption affinity of the Tp–Azo–COF coating for five OCPs was primarily affected by the halogen bond and hydrophobicity interaction. The extraction efficiencies of the Tp–Azo–COF coating for five OCPs were higher than those of three commercial SPME fiber coatings, and the enrichment factors ranged from 1061 to 3693. When combined with gas chromatography–tandem mass spectrometry, a wide linear range (0.1–1000 ng L–1), low limits of detection (0.002–0.08 ng L–1), and good fiber-to-fiber accuracy (4.3–10.9%) were achieved under optimal conditions. Moreover, the applicability of the developed method was evaluated by analyzing four samples (milk, green tea, tap water, and well water), and the recoveries were in the range of 83.4–101.6%, with relative standard deviations <8.6%. This research extends the application of the stabilized ketoenamine COF as a sample enrichment probe for OCP analysis.