共价有机框架衍生多孔碳固相微萃取纤维结合气相色谱法测定水样中的邻苯二甲酸酯

Determination of Phthalates in Water by Covalent Organic Framework Derived Porous Carbon Solid Phase Microextraction Fiber Combined with Gas Chromatography

以4-甲酰基苯硼酸(FPBA)和2,4,6-三(4-氨基苯基)-1,3,5-三嗪(TAPT)为单体,通过溶剂热法制备了共价有机框架(COF)FPBA-TAPT,将其直接热解后获得衍生多孔碳材料(PC)FTPC.傅里叶变换红外光谱(FTIR)、X射线衍射(XRD)、拉曼光谱及扫描电子显微镜(SEM)表征结果显示,该材料呈球形,表面呈褶皱结构,比表面积为499 m2/g.利用溶胶-凝胶法将其涂覆在不锈钢丝表面制得固相微萃取纤维,结合气相色谱法建立了测定水样中邻苯二甲酸酯(PAEs)的方法.对萃取和解吸条件进行优化后,该方法具有较宽的线性范围(0.5~100μg/L)、较低的检测限(0.018~0.106μg/L)和良好的稳定性(相对标准偏差,RSD≤7.8%).将该方法用于3种水样中PAEs的检测,低(5μg/L)、中(10μg/L)及高(50μg/L)加标回收率为79.5%~123.9%,RSD为1.1%~12.2%,表明该方法具有良好的准确性,可实现水体中PAEs的有效定量分析.

The covalent organic framework(COF)FPBA-TAPT was synthesized with 4-formylphenylboronic acid(FPBA)and 2,4,6-tris(4-aminophenyl)-1,3,5-triazine(TAPT)as monomer by the solvothermal reaction.Then the porous carbon material(FTPC)was prepared by direct pyrolysis of FPBA-TAPT precursor.The FTPC was then characterized using Fourier transform infrared spectroscopy(FTIR),X-ray diffractometer(XRD),Raman spectrum and scanning electron microscopy(SEM).The results showed that the material was spherical and its surface was wrinkled.Its specific surface area is 499 m2/g.It served as a coating modified on the surface of stainless steel wire by sol-gel technique to obtain a solid phase microextraction(SPME)fiber to determine phthalates(PAEs)in water samples coupled with gas chromatography.Under the optimized conditions,the method has a wide linear range(0.5—100μg/L),low limits of detection(0.018—0.106μg/L),and good stability(RSD≤7.8%).The method was applied to detecting PAEs in three water samples.The spiked recoveries of low(5μg/L),medium(10μg/L)and high(50μg/L)were 79.5%—123.9%and relative standard deviation(RSD)was 1.1%—12.2%,indicating that the method has a good accuracy and can achieve an effective quantitative analysis of PAEs in water.