Development of ZIF-67 derived hollow multishelled structures Co3O4/carbon nanomaterials as spiral solid-phase microextraction fiber for superior capture of fifteen PAHs

[Display omitted] •ZIF-67 derived hollow double-shelled Co3O4/carbon (HoMS-Co3O4) were successfully prepared.•A novel spiral-solid phase microextraction (S-SPME) fiber using HoMS-Co3O4 as coating was designed.•Open a new way for the preparation of hollow multishelled structure using ligand conversion method.•The proposed method provided a new, effective and low-cost method for rapid and superior capture PAHs. Here, a unique spiral-solid phase microextraction (S-SPME) fiber using ZIF-67 derived hollow multishelled structures Co3O4/carbon nanomaterials (HoMS-Co3O4/C) as the coating was designed for superior capture of trace polycyclic aromatic hydrocarbons (PAHs). The ligand 2-methylimidazole of ZIF-67 was replaced twice with 2,5-dihydroxyterephthalic acid and followed by pyrolysis to obtain the material with an unique hollow double-shelled structure. The formation of the hollow structure can be explained by the Ostwald ripening. Fifteen PAHs, four brominated flame retardants (BFRs), and seven endocrine chemicals (EDCs) were used to investigate the extraction performance of HoMS-Co3O4/C coated S-SPME fiber. The spiral fiber displayed higher selectivity for PAHs compared with BFRs and EDCs. The methods had low detection limits (0.002–2.680 μg L−1), wide linear ranges (0.005–1000 μg L−1), and good reproducibility (0.7–10.7%, fiber to fiber). In addition, the S-SPME fiber demonstrated excellent enrichment ability and extraction efficiency for PAHs compared with commercial SPME fibers, it might since there were strong π-π stacking force, hydrophobic interaction between analytes and HoMS-Co3O4/C coating, also the HoMS coating and the spiral fiber could greatly increase the contact area between adsorbent and target compounds. Finally, the HoMS-Co3O4/C coated S-SPME fiber had been further adopted to detect fifteen PAHs in environmental water samples successfully.