A two-step ZnO nanoparticle-directed method has been implemented to prepare polymer monolith/zeolitic imidazolate framework (ZIF) solid-phase microextraction (SPME) fiber coatings with hierarchical micro-meso-macroporosity. The polymer/ZIF monolith was prepared on the surface of a stainless steel wire from a polymerization mixture containing dispersed ZnO nanoparticles. The embedded ZnO nanoparticles in the precursor polymer monolith coating were converted on-fiber to submicrometric porous crystals of the prototypical ZIF-8, based on the coordination of Zn(II) with 2-methylimidazole. The polymer/ZIF monolith coating was applied to the headspace SPME of benzene, toluene, ethylbenzene, and xylenes (BTEX) from water samples, followed by gas chromatography-flame ionization detection (GC-FID). Hierarchically porous polymer/ZIF monolithic coatings showed a superior performance for BTEX extraction in comparison to coatings based on pure macroporous organic polymer monoliths, silicone glue/ZIF-8 coatings or commercial PDMS coatings. Experimental parameters such as desorption temperature, desorption time, salt concentration, temperature effect, equilibrium time and extraction time were investigated. Under the selected experimental conditions, limits of detection of 0.02–0.11 μg L−1, linear ranges of 0.2–200 μg L−1, relative standard deviations of 4.3–8.2%, and a fiber-to-fiber reproducibility of 8.9–9.8% (n = 3) were obtained. Recoveries higher than 88% were obtained for BTEX analysis in tap water, wastewater and landfill leachates.
