Superficially capped amino metal-organic framework for efficient solid-phase microextraction of perfluorinated alkyl substances

Perfluorinated alkyl substances (PFASs) were ubiquitously in the surface and groundwater. It is crucial and urgent to develop a rapid and ultrasensitive analysis method for the quantification of trace-level PFASs. Herein, a highly hydrophobic sorbent by capping phenylsilane groups on the surfaces of NH2-UiO-66(Zr) nanocrystals was used for efficient solid-phase microextraction (SPME) of PFASs in water samples. It was found that the superficially capped nanocrystals (NH2-UiO-66(Zr)-hp) exhibited both faster extraction kinetics and higher enrichment capacity than the non-capped nanocrystals. The extraction of eleven kinds of PFASs by NH2-UiO-66(Zr)-hp fiber reached equilibrium in 20 min. The enrichment factors of the NH2-UiO-66(Zr)-hp fiber ranged from 6.5 to 48, with a preference for long-chain PFASs over short-chain PFASs. It was proposed that superficial capping eliminated competitive moisture adsorption on the surfaces of the non-capped nanocrystals, thus facilitating the adsorption of PFASs through hydrophobic interaction. By using this new sorbent, the limits of detection of the SPME method as low as 0.035 to 0.616 ng·L-1 were achieved for the target PFASs. The recoveries of PFASs in the environmental water samples were 80.9%-120%. This study presents a new strategy for developing an efficient sorbent for PFASs by surface hydrophobic modification.