Development of a novel porous cobalt, phosphorus and nitrogen co-doped carbonaceous coating by phosphiding ZIF-67 grown on nitinol fiber for selective solid-phase microextraction of polycyclic aromatic hydrocarbons from water samples

Abstract

The nature and fabrication of the fiber coatings with good adsorption capacity and selectivity play a decisive role in solid-phase microextraction (SPME). In this work, a facile strategy was proposed to fabricate a cobalt, phosphorus and nitrogen co-doped carbonaceous (Co–P–NC) coating on superelastic nitinol (NiTi) substrate as a binder-free fiber for SPME. In particular, direct electrochemical in situ growth of ZIF-67 crystals served as the N-containing carbon precursor and sacrificial template for subsequent controllable conversion of ZIF-67 into a novel porous Co–P–NC coating on the NiTi wire substrate via a phosphiding process in a N₂ atmosphere. The obtained NiTi wire with the Co–P–NC coating (NiTi@Co–P–NC) was employed to investigate the adsorption of some representative aromatic analytes in water samples for the first time coupling with high-performance liquid chromatography with UV detection (HPLC/UV). The results proved that the resulting fiber showed superior adsorption selectivity for polycyclic aromatic hydrocarbons (PAHs). Therefore, the key parameters were further examined for the adsorption and preconcentration of PAHs. Under the obtained conditions, linear chromatographic responses were achieved over the concentration ranges of 0.03–100 μg L⁻¹ with the correlation coefficients ranging from 0.9980 to 0.9991. Limits of detection (LODs) were between 0.007 and 0.149 μg L⁻¹ (S/N = 3). The developed SPME-HPLC/UV method was applied to selective preconcentration and sensitive determination of PAHs in water. Moreover, this fiber had good fiber preparation reproducibility and presented 120 adsorption and desorption cycles at the same time in practical SPME application.