二维片层卟啉基共价有机框架材料修饰电极用于污水中汞离子的高灵敏检测  

Two-dimensional Lamellar Porphyrin-based Covalent-Organic Framework Modified Electrode for Highly Sensitive Detection of Mercury Ions in Sewage

作　　者：彭灿伟 汪莉[1] 陈受惠[1] PENG Can-Wei;WANG Li;CHEN Shou-Hui(College of Chemistry and Chemical Engineering,Jiangxi Normal University,Nanchang 330022,China)

机构地区：[1]江西师范大学化学化工学院,南昌330022

出　　处：《分析化学》2022年第3期356-364,共9页Chinese Journal of Analytical Chemistry

基　　金：国家自然科学基金项目(Nos.21765009,21964010,21465014,21665012);江西省教育厅研究生创新基金项目资助。

摘　　要：基于5,10,15,20-四(4-氨基苯)卟啉(TAPP)和对苯二甲醛(TPAL)间的胺醛缩合反应,合成了一种卟啉基共价有机框架材料(TAPP-TPAL-COF)。此材料呈多孔二维片层状,具有四边形拓扑结构和平面共轭π键。TAPP-TPAL-COF上丰富的π键可与玻碳电极(GCE)表面发生π-π共轭作用,被稳定地固载于电极表面。材料的多孔结构有利于Hg^(2+)的传输,并且卟啉环上的4个N原子可与Hg^(2+)发生配位作用,使溶液中的Hg^(2+)富集于电极表面,从而提高传感器的灵敏度。基于TAPP-TPAL-COF修饰GCE构建了一种Hg;电化学传感器,线性范围为10.9 nmol/L~17.5μmol/L,检出限为3.3 nmol/L,灵敏度为111.5μA·L/(μmol·cm^(2)),仅需250 s即可完成检测。构建的TAPP-TPAL-COF传感器具有稳定性好、灵敏度高、线性范围宽、检出限低、响应速度快的特点,为现场实时检测重金属离子提供了一种可选方案。A two-dimensional porphyrin-based covalent-organic framework(TAPP-TPAL-COF)was prepared by the amine-aldehyde condensation reaction of terephthalaldehyde(TPAL)and 5,10,15,20-tetrakis(4-aminobenzene)porphyrin(TAPP).TAPP-TPAL-COF was porous two-dimensional nanosheets with quadrilateral topological structure and planar conjugatedπbonds.The material hadπ-πconjugate interaction with the glassy carbon electrode,making the material stably immobilized on the surface of the electrode.The porous structure of TAPP-TPAL-COF was conducive to the transmission of mercury ions(Hg^(2+)),and the four N atoms in the porphyrin ring served as Hg^(2+) coordination sites to enrich Hg^(2+) in the solution on the electrode surface,improving the sensitivity of the sensor.An Hg;electrochemical sensor was thus constructed via TAPP-TPAL-COF.The linear range of the sensor was 10.9 nmol/L-17.5μmol/L,the limit of detection was 3.3 nmol/L(S/N=3),and the sensitivity was 111.5μA·L/(μmol·cm^(2)).It took only 250 s to get the current response signals.The sensor presented good stability,high sensitivity,wide linear range,low detection limit and fast response,providing an optional solution for real-time detection of heavy metal ions in water samples.

关 键 词：汞离子 共价有机框架 二维片层卟啉 电化学传感器 微分脉冲溶出伏安法 污水分析 

分 类 号：O657.1[理学—分析化学] X832[理学—化学]