基于表面等离激元介孔材料对POPs吸附富集效应的SERS定量痕量检测

In this project, based on the previous studies in my group upon the preparation of mesoporous materials using nanocasting protocol and their applications in plasmonic areas, we plan to investigate the adsorption and preconcentration effect of surface-enhanced Raman spectroscopy (SERS) active-mesoporous materials on persistent organic pollutants (POPs) molecules by means of their surface functionalization, thus solve the issue of low sensitivity on typical POPs molecule detection via SERS technique. Firstly, the Au and MoO2 mesoporous structures are prepared using ordered mesoporous silica as hard template by means of the nanocasting protocol. The control principle of pore structure, pore sizes, and components in mesoporous materials during nanocasting processes will be in-depth investigated, and the new growth mechanism of nanocrystals in a confined space, i.e., mesoporous channels, will be revealed. Secondly, by means of the electromagnetic field calculation and the measurement of SERS performance, the basic rules of interaction between mesoporous structure and light, and the mechanism of resulted huge electromagnetic enhancement will be revealed. Thirdly, by means of the surface functionalization of mesoporous materials, the adsorption and preconcentration effect on several kinds of POPs molecules can be realized. Thus, from molecule level, the interactions, basic principle and the corelation among the functionalization molecule, POPs molecules as well as the surface of mesoporous materials, will be understood. This proposal is expected to obtain a remarkable SERS technique, displaying an on-site, fast, quantitative, super sensitive detection, hence has important academic value and application prospect.

本项目在我组关于介孔材料纳米铸造法制备及其在表面等离激元领域应用基础上，拟通过对具有高SERS活性的介孔材料表面功能化设计，获得对POPs分子的吸附富集效应，来解决SERS技术对POPs分子检测灵敏度低的问题。首先，以有序介孔SiO2为模板，通过纳米铸造法制备金及MoO2介孔结构，研究纳米铸造过程中介孔材料孔结构、孔径大小、材料组分调控的基本规律，揭示纳米晶在分子筛受限空间内晶体生长新机制。其次，通过电磁场理论计算及SERS性能测试，揭示介孔结构与光相互作用的基本规律及产生巨大电磁场增强作用的物理本质。然后通过对介孔材料表面功能化设计，实现对几类典型POPs分子的高效吸附富集，从分子水平上深入理解表面修饰分子与POPs分子及介孔材料表面之间相互作用的基本规律和相关性。有望开发出基于SERS技术对典型POPs分子的现场、快速、定量、超灵敏检测新技术。因此，本研究具有重要的学术价值和应用前景。

本项目在我组关于介孔材料纳米铸造法制备（代表性工作发表在Nature Communications, 2018, 9, 521上）及其在表面等离激元领域应用基础上，通过对具有高SERS活性的介孔材料表面功能化设计，获得了对POPs分子的吸附富集效应，解决了SERS技术对POPs分子检测灵敏度低的关键科学技术问题。首先，以有序介孔SiO2为模板，通过纳米铸造法制备了金介孔结构，研究了纳米铸造过程中介孔材料的孔结构、孔径大小、材料组分调控的基本规律，揭示了纳米晶在分子筛受限空间内晶体生长新机制。其次，通过电磁场理论计算及SERS性能测试，揭示了介孔结构与光相互作用的基本规律及产生巨大电磁场增强作用的物理本质。通过对介孔材料表面功能化设计，实现了对几类典型POPs分子的高效吸附富集，从分子水平上深入的理解了表面修饰分子与POPs分子及介孔材料表面之间相互作用的基本规律和相关性。开发出可基于SERS技术对典型POPs分子的现场、快速、定量、超灵敏检测新技术。.本项目执行期间，基于对POPs分子的深入了解，我们在浓缩富集及增强光谱检测领域获得了其他重要研究工作进展。基于对胶体纳米颗粒干燥过程以及“咖啡环”效应的深入理解和实验研究，我们提出了提出一种新颖的轻质漂浮颗粒方案，该方案在液滴干燥过程中能够完全消除“咖啡环”效应的出现，从而实现探测分子的高度浓缩富集及空间定位。受微孔β-环糊精与有机污染物形成主客体包覆的启发，提出了一种对POPs分子的快速吸附-解吸附的浓缩富集新策略，并实现了对有机污染物分子的超灵敏快速检测。.本项目相关成果在Nature Communications, 2021, 12, 6849；Nature Communications, 2020, 11, 2603，Analytical Chemistry等期刊发表SCI论文26篇，申请国家发明专利2项，16篇论文SCI引用超过560余次。做国际国内学术会议邀请报告4次，担任光散射学报期刊副主编，产生了广泛的学术影响。研究成果得到了包括美国麻省理工的Robert Langer教授、中科院院士江雷教授在Advanced materials、Advanced Science、Nature Communications等权威期刊的引用和高度评价。