Journal
JOURNAL OF HAZARDOUS MATERIALS
Volume 397, Issue -, Pages -Publisher
ELSEVIER
DOI: 10.1016/j.jhazmat.2020.122793
Keywords
covalent organic framework; microwave reaction; solid phase micro-extraction; perfluorinated substance; water sample
Categories
Funding
- National Natural Science Foundation of China [31972145, 21372147]
- Undergraduate Innovative Research Training Program [S201910445004]
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To synthesize covalent organic framework (COF) via irreversible reactions is more challenging than by reversible ones. In this work, microwave-assisted synthesis is used to facilitate the nucleophilic substitution of 2,3,5,6-tetrafluoro-4-pyridinecarbonitrile with 2,3,6,7,10,11-hexahydroxy triphenylene. The dioxin-linked COF, named TH-COF, was efficiently synthesized with extraordinarily large surface area of 1254 m(2) g(-1). With its high crystallinity, excellent thermal and chemical stabilities, TH-COF is used as the coating for the solid-phase microextraction (SPME) of perfluorinated alkyl substances (PFASs). The adsorptive mechanism was evaluated with adsorption isotherm and kinetic adsorption. Adsorption energies are calculated based on the density functional theory. Following SPME with TH-COF-coated fibers, PFASs were eluted using 1 mL of 0.6% trifluoroacetic acid/methanol and analyzed through the ultra-performance liquid chromatography equipped with triple quadrupole mass spectrometer (UPLC-MS/MS). When applied to spiked real water samples, this method demonstrates good linearity (0.01-1000 ng L-1) with R-2 >= 0.9945. The TH-COF-SPME-UPLC-MS/MS technique provides low limits of detection (0.0020-0.0045 ng L-1), excellent precision (<= 7.9%), and good fiber-to-fiber reproducibility (<= 7.1%). The TH-COF-coated fibers can be reused at least 20 times without the loss of extraction performance. In addition, the relative recoveries from spiked real water samples are 89.5%-105%.
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