色谱

色谱 ›› 2026, Vol. 44 ›› Issue (4): 383-392.DOI: 10.3724/SP.J.1123.2025.07004

• 研究论文 • 上一篇    下一篇

磁性氟化共价三嗪骨架材料用于高效萃取全氟化合物

张文敏1,2, 刘冠城2, 方敏1, 郭军凌1, 张兰2,*()   

  1. 1.闽江师范高等专科学校，福建 福州 350108
    2.福州大学，福建 福州 350116
  • 收稿日期:2025-07-07 出版日期:2026-04-08 发布日期:2026-04-13
  • 通讯作者: * Tel：0591-22866135，E-mail：zlan@fzu.edu.cn.
  • 基金资助:
    国家自然科学基金项目(22374023);福建省自然科学基金项目(2023J05085)

Magnetic fluorinated covalent triazine frameworks for efficient extraction of perfluorinated compounds

ZHANG Wenmin1,2, LIU Guancheng2, FANG Min1, GUO Junling1, ZHANG Lan2,*()   

  1. 1. Minjiang Teachers College，Fuzhou 350108，China
    2. Fuzhou University，Fuzhou 350116，China
  • Received:2025-07-07 Online:2026-04-08 Published:2026-04-13
  • Supported by:
    National Natural Science Foundation of China(22374023);Natural Science Foundation of Fujian Province(2023J05085)

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摘要：

全氟化合物（PFCs）是一种新型的持久性有机污染物，消费者摄入PFCs污染的软饮料后，会引起严重的系统性疾病。然而，软饮料中PFCs的含量极低且基质复杂，直接利用高效液相色谱-串联质谱（HPLC-MS/MS）进行含量测定比较困难，因此在仪器分析之前需要对样品进行必要的前处理。本研究通过一锅法成功制备了一种磁性氟化共价三嗪骨架材料（Fe2O3/CTF-F），并将其作为磁性固相萃取（MSPE）技术的吸附剂，用于7种PFCs的高效萃取。同时，系列表征结果显示Fe2O3/CTF-F拥有高比表面积（1 452.3 m2/g）、高孔隙度（0.82 cm3/g）、高含氟量（17.50%）和强磁响应性（7.1 emu/g），可以提供大量的可接触吸附位点、高亲和的氟-氟作用力以及快速的磁性分离能力，对PFCs表现出优异的萃取能力。随后，通过单因素实验，优化了吸附剂的用量、提取时间、洗脱溶剂和洗脱时间等MSPE过程中的关键条件，并将其与HPLC-MS/MS技术相结合，建立了一种用于软饮料中PFCs分析的新方法。所建立的分析方法具有线性范围宽（0.008~250.0 pg/mL）、线性相关性高（R≥0.999 2）、检出限低（0.002~0.005 pg/mL）、重复性良好（RSD≤8.2%， n=5）等优点。最后，通过所建立的分析方法对5种软饮料样品进行了分析，并且在所有样品中均检测出了超痕量的PFCs，含量范围为3.5~54.6 pg/mL。实验结果表明，Fe2O3/CTF-F是一种极具潜力的吸附剂，可用于PFCs的高效萃取，同时所建立的分析方法也适用于软饮料中PFCs的高灵敏检测。

关键词: 共价三嗪骨架, 全氟化合物, 磁性固相萃取, 高效液相色谱-串联质谱

Abstract:

Perfluorinated compounds （PFCs） are a new type of persistent organic pollutants. When consumers consume soft drinks contaminated with PFCs， it can cause severe systemic diseases. Increasing concern regarding the presence of PFCs in soft drinks has resulted in the need for reliable analytical methods for the monitoring of PFCs. However， the content of PFCs in soft drinks is extremely low and the matrix is complex， making it difficult to directly determine their content using high performance liquid chromatography-tandem mass spectrometry （HPLC-MS/MS）. Therefore， the necessary sample pretreatment is required before instrumental analysis. Magnetic solid-phase extraction （MSPE） is a simple， rapid， and efficient solid-liquid separation technique， and its extraction efficiency depends on the characteristics of the magnetic adsorbent. Covalent triazine frameworks （CTFs） are porous organic polymers connected by triazine bonds. They have the characteristics of large specific surface area， rich pore structure， adjustable functionality， good chemical stability and thermal stability， making them widely used in sample pretreatment. In this study， a magnetic fluorinated covalent triazine framework material （Fe2O3/CTF-F） was prepared by a one-pot method and characterized in detail. The X-ray photoelectron spectra （XPS）， Fourier-transform infrared （FT-IR） spectrum， and X-ray diffraction （XRD） pattern demonstrated the successful synthesis of Fe2O3/CTF-F with a high fluorine content （17.50%）， which was formed through tetrafluoroterephthalonitrile polymerization and hydrated ferric chloride decomposition. The highly fluorinated material can provide a specific and strong affinity for PFCs through fluorous-fluorous （F-F） interactions. The experimental results of nitrogen adsorption-desorption and magnetic properties showed that the Fe2O3/CTF-F has a high specific surface area （1 452.3 m2/g） and porosity （0.82 cm3/g）， as well as a strong magnetic responsivity （7.1 emu/g）. It indicates that the Fe2O3/CTF-F possesses a large number of accessible adsorption sites and a rapid magnetic separation capability， providing a guarantee for efficient extraction of PFCs. Subsequently， the Fe2O3/CTF-F was used as an adsorbent for MSPE technology for the efficient extraction of seven PFCs. Because of its many accessible adsorption sites and strong fluorine-fluorine interactions， the Fe2O3/CTF-F showed excellent extraction ability for PFCs. Finally， by combining the MSPE method with HPLC-MS/MS technology， a new analytical method was established for the analysis of PFCs in soft drinks. To achieve the best performance， single-factor experiments were conducted to optimize the dosage of the adsorbent， the extraction time， the elution solvent and elution time in the MSPE process. Under the optimal conditions， the established analytical method has the advantages of wide linear ranges （0.008–250.0 pg/mL）， high linear correlations （R≥0.999 2）， low LODs （0.002–0.005 pg/mL）， and good repeatability （RSDs≤8.2%， n=5）. The established analytical method was then used to analyze five kinds of soft drink samples， and ultra-trace amounts of PFCs were detected in all samples， with contents ranging from 3.5 to 54.6 pg/mL. Among them， the highest content of perfluorooctanoic acid （PFOA） measured was 54.6 pg/mL， and its content did not exceed the limit stipulated in the national standard GB 5749-2022 （80 pg/mL）. Besides， the established analytical method was also compared comprehensively with other reported methods. The established method only requires a small amount of adsorbent （5.0 mg）， and can achieve a low detection limit （0.002 pg/mL） after a short pretreatment time （20 min）. The comparison results indicate that the established method has the advantages of being rapid， sensitive， and accurate， and can be used for the monitoring of PFCs in soft drinks. Meanwhile， the preparation method of the Fe2O3/CTF-F in this study is very simple and convenient， which is conducive to the transformation and application of this method. In conclusion， the Fe2O3/CTF-F is a highly potential adsorbent for the efficient extraction of PFCs， and the established analytical method is also suitable for the high-sensitivity detection of PFCs in soft drinks.

Key words: covalent triazine framework （CTF）, perfluorinated compounds （PFCs）, magnetic solid-phase extraction （MSPE）, high performance liquid chromatography-tandem mass spectrometry （HPLC-MS/MS）

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