多功能磁性MOFs固定化两亲性离子液体的制备及在大气污染物监测中的应用基础研究

Air pollution has become a major livelihood issue facing by the Government to be solved urgently. This project aims to design and synthesis a kind of novel core-shell efficient magnetic MOFs（Metal-Organic Framework Materials）amphiphilic supported ionic liquids (M-ASILs@MOFs) by the conjugate-ligands directed self-assembly method, by which the functional amphiphilic ionic liquid was bonded to the surface of the magnetic Fe3O4 particles functionalized modifications. Considering the sorption/desorption kinetics data obtained from six groups of common atmospheric pollutants (sulfur compounds, nitrogen compounds and polycyclic aromatic hydrocarbons, etc.), as well as combination with the material properties (i.e.the composition, the shape, and the paticle size, etc.), the relationship between the preparation paratmers (such as ultrasonic wave) and the adsorption/desorption properties of M-ASILs@MOFs are discussed in detail. The intrinsic relationship between the M-ASILs@MOFs microstructure with the adsorption/desorption properties and amphiphilic will be investigated, the semi-empirical mathematical model will be proposed. The adsorption/desorption microscopic mechanisms between M-ASILs@MOFs and atmospheric pollutants will be revealed. Based on the above studies, a controllable method for the synthesis of M-ASILs@MOFs will be proposed. Additionally, a rapid, accuate and sensitive analytical system for the determination of six groups of trace common air pollutants by thermal desorption or online magnetic separation/chromatography - mass spectrometry will be established. The research findings will not only lay a solid scientific foundation on health and safety assessment, but also play an important scientific significance for the control and prevention of air pollutants.

大气污染已成为当今政府急需解决的重大民生问题。本项目拟通过对磁性Fe3O4微粒的表面功能化修饰，采用共轭配体导向自组装方法将功能化两亲性离子液体键合到磁性微粒表面来制备新颖的核-壳结构的磁性MOFs固定化两亲性离子液体（M-ASILs@MOFs）。同时，根据硫化物、含氮化合物和多环芳烃等6类常见大气污染物的吸附/脱附动力学数据，结合材料形状、尺寸和组成等特征参数，研究超声强化等制备条件对材料微观特征和吸附/脱附性能的内在影响，及其与两亲性和磁特性之间的内在联系，构建半经验数学模型，揭示M-ASILs@MOFs与大气污染物分子之间的吸附/脱附等微观作用机制，实现M-ASILs@MOFs的可控制备，并构建快速、灵敏、准确的6种常见大气污染物的热解吸/在线磁控分离-色/质谱联用检测技术体系。研究成果不仅可为大气污染物的健康安全评估奠定科学基础，而且对大气污染物的防控具有重要的科学意义。

大气污染已成为当今政府急需解决的重大民生问题。本项目通过对磁性Fe3O4微粒的表面功能化修饰，采用共轭配体导向自组装方法将功能化离子液体键合到磁性微粒表面来制备新颖的2,4-二硝基苯肼-固定化离子液体磁性MOFs复合材料（DNPH-MOFs@ILs）和MOFs复合材料（NH2-Fe/Zr/Ni-MOFs、NH2-Fe/Zr/Mn-MOFs）。采用透射电镜等分析手段表征了制备材料的组成、形状、尺寸、孔径和表面修饰等特征参数，结合制备条件和吸附净化数据，探讨了功能化DNPH-MOFs@ILs和MOFs复合材料（NH2-Fe/Zr/Ni-MOFs、NH2-Fe/Zr/Mn-MOFs）的制备方法，研究了功能化DNPH-MOFs@ILs微观结构对富集净化的影响，开展了环境水样及污泥中目标污染物的提取及污泥脱水机理的研究。项目不但研发建立了大气环境污染物小分子醛的液相色谱串联质谱检测方法，而且还建立了一系列复杂基质中有毒有害化学物如氨基甲酸酯类农药、五氯酚、N-甲基亚硝胺、苯巴比妥和维生素D2等残留的富集净化及其液相色谱/串联质谱检测技术体系。项目共发表论文13篇（其中SCI收录论文7篇），共申请澳大利亚革新专利2件（已授权2件），共申请国家发明专利11件（已授权发明专利3件），培训专业技术人员389名，受益机构80多家，项目部分内容分获浙江省科技进步奖三等奖和中华预防医学会科学技术奖三等奖各1项。项目成果可为大气环境和水环境污染的风险评估奠定科学的基础，对大气环境和水环境的污染防控具有重要的科学意义。