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Ordered macro/micro-porous metal-organic framework of type ZIF-8 in a steel fiber as a sorbent for solid-phase microextraction of BTEX

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Abstract

An ordered array of macropores on microporous metal-organic framework crystals was developed. This array facilitates analyte diffusion in microextraction applications. A prototypical zeolitic imidazolate framework (ZIF-8) was synthesized in the interstitial voids of a polystyrene bead packing of sub-μm polystyrene beads. After removal of polystyrene by dimethylformamide, a single-crystal ordered macroporous ZIF-8 material (SOM-ZIF-8) was obtained. The resulting μm-sized SOM-ZIF-8 crystals are based on a fully-microporous structure containing a macroporous network. The SOM-ZIF-8 crystals were placed in a stainless-steel fiber and applied as a sorbent for the extraction of benzene, toluene, ethylbenzene, and xylenes (BTEX) by headspace solid-phase microextraction (HS-SPME). The fiber was applied to the HS-SPME of BTEX from wastewater samples followed by GC with flame ionization detection. A Plackett-Burman design and Box-Behnken design were carried out to evaluate the variables affecting the method. Figures of merit include (a) limits of detection of 1.0–12 ng·L−1, (b) linear ranges of 0.004–50 μg·L−1, (c) relative standard deviations of 4.6–6.7%, and (d) excellent fiber-to-fiber reproducibility (5.6–6.7% for n = 3). Spiking recoveries between 92 and 106% were obtained for BTEX analysis in wastewater samples. The introduction of an ordered macroporous network on microporous ZIF-8 crystals enhanced analyte uptake. This increases the extraction performance by a factor of 2.5–3.1 when compared to analogous ZIF-8 crystals that lack templated macropores.

BTEX extraction is enhanced by templating an ordered macroporous network in microporous crystals as exemplified with the single-crystal ordered macropore zeolitic imidazolate framework-8 (SOM-ZIF-8).

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Acknowledgements

The financial support of this project by University of Mazandaran is gratefully acknowledged.

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Authors and Affiliations

  1. Australian Centre for Research on Separation Science (ACROSS), School of Natural Sciences-Chemistry, University of Tasmania, Private Bag 75, Hobart, TAS, 7001, Australia

    Fernando Maya

  2. Department of Analytical Chemistry, Faculty of Chemistry, University of Mazandaran, P.O. Box 57416-13534, Babolsar, Islamic Republic of Iran

    Milad Ghani

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Maya, F., Ghani, M. Ordered macro/micro-porous metal-organic framework of type ZIF-8 in a steel fiber as a sorbent for solid-phase microextraction of BTEX. Microchim Acta 186, 425 (2019). https://doi.org/10.1007/s00604-019-3560-0

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