Facile synthesis of fluorine-functionalized long-chain metal–organic frameworks for highly efficient enrichment and sensitive detection of bisphenols in water samples

Abstract

The exceptional stability of long-chain metal–organic framework materials (MOFs) is crucial for preserving their adsorption capabilities and practical applications. Herein, a well-defined material (50.0 %4F-BDC@UiO-67) with enhanced stability and pollutant adsorption was successfully synthesized through a straightforward one-step method, utilizing Zr⁴⁺ as the metal ion and employing 4,4′-biphenyldicarboxylic acid, which contains two benzene rings, alongside tetrafluoroterephthalic acid (4F-BDC), which contains one benzene ring, as dual ligands. The 50.0 %4F-BDC@UiO-67 material was utilized for the enrichment of harmful bisphenol pollutants (BPs) from the environment. Experimental results demonstrated that the synthesized 50.0 %4F-BDC@UiO-67 sorbent exhibited significantly improved adsorptive capacity, with its enrichment performance for BPs being 1.5–6.3 times greater than that of pristine UiO-67. The interactions between the material and BPs were explored using density functional theory calculations and experimental characterization. Findings indicated that the incorporation of fluorine enhanced the π–π and coordination interactions between 50.0 %4F-BDC@UiO-67 and BPs, while also introducing additional hydrogen bonding interactions. This outcome offers insights for the future design of materials with superior enrichment capabilities. Leveraging multiple synergistic forces, and in conjunction with high-performance liquid chromatography-diode array detection, the developed method exhibited a broad linear range (0.1–200 ng mL⁻¹), excellent correlation coefficients (0.9992–0.9996), and low detection limits (0.1–0.5 ng mL⁻¹) for BPs. Satisfactory recoveries were achieved for actual water samples (82.9–105.9 %). This work presents a strategy for enhancing the stability and adsorption performance of long-chain MOFs.