Institute of Food Safety and Environment Monitoring, Fuzhou University, Fuzhou, 350108, China.
Forensic Science Division, Fujian Provincial Department of Public Security, Fuzhou, China.
Talanta. 2021 Aug 15;231:122343. doi: 10.1016/j.talanta.2021.122343. Epub 2021 Apr 16.
Covalent organic frameworks (COFs) showed great promise in effective adsorption of target molecule via size selectivity. Although various magnetic 2D COFs composites have been studied and exhibited the intensive applications, the incorporation of 3D COFs and magnetic nanoparticles to form a new class of magnetic adsorbents with enhanced function still has no reports. Herein, a novel FeO@3D COF with heteroporous structure matching to the sizes of bisphenol A (BPA) was firstly synthesized for better adsorption of BPA than common magnetic 2D-COFs. Three FeO@3D COFs nanospheres were synthesized under the solvothermal conditions in autoclave, and the optimum FeO@3D-COF denoted as FeO@COF-TpTAM (Tp, 1,3,5-triformylphloroglucinol; TAM, tetra(p-aminophenyl)-methane) was selected and employed. Detailed characteristics of FeO@COF-TpTAM were evaluated via various techniques including TEM, FTIR, TGA, XRD and BET. Excellent chemical and thermal stability, high surface area (294.6 m g) and pore volume (0.2 m g) with multiple pore sizes comparable with the simulated three-dimensional sizes of BPA were exhibited. A high adsorption capacity of BPA up to 209.9 mg/g that was better than common 2D-COFs was achieved, and the sensitive MSPE-LC-MS method with wide linear range (10-5000 pg/mL), low detection limit (4 pg/mL, S/N = 3) was built. Satisfactory recoveries of BPA as 93.8 ± 1.4%-101.4 ± 5.1% (n = 3) and 100.4 ± 1.9% ~ 107.3 ± 1.2% (n = 3) were obtained in milk and river water samples, respectively. This work demonstrates the promising application of FeO@3D COF as efficient adsorbents of trace BPA, and opens up a new access for the efficient MSPE in sample pretreatment for food or environmental safety analysis.
共价有机骨架（COFs）通过尺寸选择性在有效吸附目标分子方面表现出巨大的潜力。尽管已经研究了各种磁性二维 COFs 复合材料，并表现出了广泛的应用，但将三维 COFs 和磁性纳米颗粒结合起来形成具有增强功能的新型磁性吸附剂仍未见报道。在此，首次合成了具有与双酚 A（BPA）尺寸相匹配的杂孔结构的新型 FeO@3D COF，以实现对 BPA 的更好吸附，优于常见的磁性二维-COFs。在高压釜中的溶剂热条件下合成了三个 FeO@3D COFs 纳米球，并选择和使用了最佳的 FeO@3D-COF 表示为 FeO@COF-TpTAM（Tp，1,3,5-三（均三嗪基）苯；TAM，四（对氨基苯基）甲烷）。通过 TEM、FTIR、TGA、XRD 和 BET 等多种技术对 FeO@COF-TpTAM 的详细特性进行了评估。它表现出出色的化学和热稳定性、高表面积（294.6 m g）和孔体积（0.2 m g）以及多个与 BPA 的模拟三维尺寸相媲美的孔径。实现了高达 209.9 mg/g 的 BPA 吸附量，优于常见的二维-COFs，建立了一种具有宽线性范围（10-5000 pg/mL）、低检测限（4 pg/mL，S/N=3）的灵敏 MSPE-LC-MS 方法。在牛奶和河水样品中，BPA 的回收率分别为 93.8±1.4%-101.4±5.1%（n=3）和 100.4±1.9%~107.3±1.2%（n=3），结果令人满意。这项工作证明了 FeO@3D COF 作为痕量 BPA 有效吸附剂的应用前景广阔，为食品或环境安全分析中样品预处理的高效 MSPE 开辟了新途径。
