MOFs/Ag-Au/硅纳米孔柱阵列SERS活性基底的制备及其对五氯苯酚的检测研究

Pentachlorophenol (PCP) can seriously damage the ecosystems of water and soil as well as human health. Therefore, it is of great significance to design accurate, rapid and sensitive PCP recognition sensors. In this project, we are devoted to design a novel MOFs/Ag-Pentachlorophenol (PCP) can seriously damage the ecosystems of water and soil as well as human health. Therefore, it is of great significance to design accurate, rapid and sensitive PCP recognition sensors. In this project, we are devoted to design a novel MOFs/Ag-Au/Si-NPA composite SERS substrate with the combination of metal-organic frameworks (MOFs) and nanoporous pillar array (Si-NPA) to achieve the rapid identification and quantitative detection of PCP. Firstly, the inclusion associations, hydrogen bond and π-π interactions between the PCP and MOFs, and the hydrophobic of the Si-NPA can enhance the selectivity and adsorption of PCP. Secondly, high sensitivity detection of PCP can be achieved based on the high SERS activity of the three-dimensional nanoporous pillar array Ag-Au/Si-NPA. The influences of different ligands and open metal sites on the sensing performances would be studied for screening a better sensor to PCP. The research results might have theoretical and practical significance for the design and assembly of novel pentachlorophenol identification sensors.

五氯苯酚（PCP）对水、土壤等生态系统及人体健康有着严重危害。因此，设计准确、快捷、灵敏的PCP识别传感器具有重要意义。本项目拟将金属有机骨架材料（MOFs）与硅纳米孔柱阵列（Si-NPA）结合设计新型MOFs/Ag-Au/Si-NPA复合SERS基底，实现对PCP的快速识别及定量检测：一、利用MOFs孔洞对PCP的包合作用、PCP与MOFs间的氢键与π-π共轭作用以及Si-NPA的疏水性提升对PCP的选择性和吸附性；二、利用三维孔柱阵列Ag-Au/Si-NPA的高SERS活性实现对PCP的高灵敏度探测。同时进一步研究开放金属位点前后以及配体结构的差异对识别性能的影响，筛选出识别性能最为优良的SERS传感器。本项目的实施将为新型PCP SERS传感器的设计及组装提供重要的数据支持和理论依据。

五氯苯酚（PCP）是一种持久性有机污染物，对水、土壤等生态系统及人体健康有着严重危害。目前常用的检测方法存在着复杂繁琐、代价高、需要对样品进行预处理、检测时间长，不利于大规模样品检测等问题。表面增强拉曼散射（SERS）作为一种快速、实时、无损原位检测技术，在化学分析、生物医学、环境治理、国防科技等领域得到了广泛应用。然而SERS仅在金、银、铜等贵金属的粗糙表面或一定距离内才具有高活性，诸如PCP之类的分析物，由于不含巯基(-SH)、氨基(-NH3)等可以与贵金属通过化学键结合的官能团，很难吸附到金属表面，因此，对这些物质进行SERS检测时探测灵敏度严重受限。金属有机骨架材料（MOFs）是一种多孔材料，因其具有超高的比表面积，可调的孔径、开放的金属位点、化学可修饰性以及对目标物的高吸附性和选择性等优点常被用于气体的储存、吸附与分离，是一类优异的物质吸附剂。因此通过将MOFs修饰在SERS基底表面对PCP之类的分析物进行富集提高SERS检测灵敏度是一种新的思路。我们通过以规则的阵列化纳米结构Si-NPA（硅纳米孔柱阵列）为衬底，采用不同方法在其上生长了具有高密度热点的Au-Ag双金属纳米颗粒，之后，对其表面进行ZIF-8修饰，构筑新型的ZIF-8/Au-Ag/Si-NPA复合SERS基底，利用ZIF-8的孔洞对PCP的包合作用、PCP与ZIF-8间的氢键与π-π共轭作用以及Si-NPA的疏水性提升对PCP的选择性和吸附性能，最终实现了对PCP的快速识别及定量检测，为PCP SERS传感器的设计提供了一定的理论依据。