摘要
An electron-deficient 3D carborane-COF (CB-TAPM) was fabricated. • CB-TAPM was used as SPME fiber coating for extraction of PAHs. • High affinity of B-rich COF fiber due to unique structure and multiple interactions. • An ultrasensitive HS-SPME/GC–MS/MS method was developed for detection of PAHs. • Greenness of the developed approach was evaluated based on various metric tools. In this study, carborane covalent organic framework (CB-TAPM) with electron-deficient structure was synthesized and applied as coating material for solid-phase microextraction (SPME) fibers. The extraction efficiency of CB-TAPM COF-coated fibers for polycyclic aromatic hydrocarbons (PAHs) was systematically evaluated and demonstrated superiority over other investigated COF-coated fibers and commercial fibers. The superior enrichment capacity and selectivity of the fabricated fibers for PAHs were attributable to unique electron-deficient boron-rich mesoporous framework and high surface area, which can provide multiple interactions (e.g. hydrophobic effects, π-π stacking, B-H δ- ···H δ+ -C and size-matching effects) with the target analytes. Under the optimized conditions, the developed SPME/GC-MS/MS method demonstrated excellent linearity for target PAHs, with determination coefficients (R²) ranging from 0.9917 to 0.9999 across the calibration curves. The method achieved detection limits (LODs, S/N = 3) of 11–15 pg g −1 for PAHs in milk and 0.24–0.36 pg mL −1 in water samples, demonstrating exceptional sensitivity for complex matrices. Additionally, the fabricated fibers exhibited high repeatability (RSD < 8.6%, n = 5), and reproducibility (inter-batch RSD < 7.8%, n = 5) and reusability (>150 extraction-desorption cycles). This study demonstrates a sustainable and novel methodology for PAH extraction and analysis, while simultaneously broadening the scope of COF-based coatings for SPME applications. Download: Download high-res image (154KB) Download: Download full-size image
危险品化学品经营许可证（带存储）