功能化介孔复合金属有机框架的制备及其对有机污染物的富集、分析检测

项目旨在合成具有超大比表面积的功能化介孔复合金属有机框架（MOFs）材料。采用大尺寸有机配体或以阳离子表面活性剂为软模板，得到具有介孔孔道的MOFs；通过纳米组装技术，制备出核壳式、镶嵌式等复合磁性MOFs或负载纳米金颗粒的MOFs；通过配位、共价修饰以及溶剂辅助配体交换等方法对介孔复合MOFs进行功能化修饰。以修饰后的介孔MOFs为固相萃取吸附剂，探讨其在环境或生物样品中有机污染物的高效萃取富集及快速检测中的应用。该类材料的超大比表面积和介孔孔道使其对有机污染物具有超高吸附容量和较快的吸附速率；介孔孔道对环境介质中大分子的蛋白质、腐殖酸等干扰物质具有尺寸排阻作用，避免了这些大量共存天然有机质对痕量目标污染物富集的干扰。将功能化介孔复合MOFs的高效萃取富集与HPLC-MS、GC-MS、MALDI-TOF-MS等检测技术联用，可以实现对环境或生物样品中微量有机污染的高效、灵敏、快速分析。

This project focuses on the synthesis of functionalized mesoporous metal-organic frameworks composites possessing ultrahigh specific surface areas. Employing large size of organic ligands or cationic surfactant as soft templates, MOFs with mesoporous structure were obtained. Based on nanoscale assembly technology, core-shell structured magnetic MOFs or MOFs loading with Au nanoparticles were prepared. The mesoporous MOFs composites were functionalized via coordination, covalent interactions, or solvent-assisted ligand incorporation. After that, the application potential of the modified mesoporous MOFs composites as solid-phase extraction adsorbents was investigated for the efficient extraction and rapid analysis of organic contaminants from environmental or biological samples. These MOFs composites have ultrahigh surface areas and uniform meso-pores, endowing extremely high adsorption capacity and fast adsorptive rate to organic pollutants. The mesopores in MOFs can prevent the macromolecules (such as humic acids, proteins) from entering by size exclusion, thus the extraction efficiency of trace level of target organic pollutants was not influenced by the abundant coexisting natural organic matter in sample matrix. Combined the excellent extraction performance of the functionalized mesoporous MOF composites to targets with the HPLC-MS, GC-MS, or MALDI-TOF-MS detection technique, the efficient, sensitive and rapid pretreatment and analysis of trace contaminants in environmental or biological samples can be achieved.