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.
