Double -shelled hollow ZnO/carbon nanocubes as an efficient solid-phase microextraction coating for the extraction of...

Efficient extraction of pollutants with different chemical properties from environmental samples has attracted great attention in the development of analytical chemistry. However, it is still a challenge to develop an appropriate and sensitive adsorbent for determining broad-spectrum analytes. Herein, zeolitic imidazole framework-8 (ZIF-8)-derived double-shelled hollow zinc oxide/carbon (ZnO/C) nanocubes were reported as a novel coating for solid-phase microextraction (SPME). The nanocubes with a unique structure and composition were obtained by controlled etching of ZIF-8 with tannic acid (TA) followed by pyrolysis. When a ZnO/C nanocube-coated fiber (ZnO/C-F) was used to extract the complex environmental samples containing both nonpolar (benzene compounds (BTEX)) and polar (chlorophenols (CPs)) pollutants, excellent extraction performance was achieved; we obtained low detection limits (0.14-0.56 ng L-1 for BTEX and 1.10-2.84 ng L-1 for CPs), good repeatability (2.2-5.9% for six replicated extractions) and excellent reproducibility (0.61-7.8%, fiber to fiber). The broad-spectrum SPME performance was ascribed to the synergistic effect between the composition and structure of ZnO/C nanocubes. Compositionally, the uniform dispersion of ZnO and carbon framework could provide abundant adsorption active sites, where Zn-OHs bound CPs by hydrogen bonding and carbon absorbed BTEX through π-π stacking interaction and hydrophobic interaction. Structurally, the double-shelled hollow morphology of the nanocubes was favorable for the sensitive extraction. Finally, the established ZnO/C-F-based headspace-SPME method was used for the preconcentration and determination of abundant analytes from real water samples. These findings open the door for the practical use of double-shelled hollow multicompositional inorganic materials.