基于MOFs光电功能材料构建的光电化学传感器及在环境微污染物检测中的应用

Endocrine disrupting chemicals (EDCs), pharmaceutical and personal care products (PPCPs), as environment micro-pollutants can endanger human and ecological system directly or indirectly, therefore, the fabrication of photoelectrochemical (PEC) sensor for determination of environmental micro-pollutants is of great significance. Due to the advantages of adjustable structure, controlled properties and devisable function, MOFs have been extensively studied in related fields. This project is devoted to the preparation of photoelectric functionalized MOFs with excellent performance by adjusting the band structure and electric conduction performance of MOFs, which achieved through organic ligand functionalization, surface modification, multistage sensitized of semiconductors and the hybrid coupling of electronic transmission medium. The obtained material was used as signal transmission matrix for the fabrication of PEC sensor in the following research. And then, the specific sensor identification models are designed by combining immune analysis, molecular recognition, aptamer analyzing technology and enzyme-labeling strategy. The PEC sensor is constructed to achieve high sensitivity, strong specificity, simple operation and low cost determination of environmental micro-pollutants. The effect of matrix material composition and structure on the photoelectric conversion efficiency, and the identification model of PEC sensor to the photoelectrocatalytic performance are further studied systematically, and the probable PEC response mechanism of the sensor are elucidated. The objectives of the study are expected to inject new vitality for the design and preparation of functional MOFs, the development and progress of PEC sensor, and the rapid detection of environmental micro-pollutants.

内分泌干扰物(EDCs)和药品及个人护理品(PPCPs)类环境微污染物直接或间接的危害人类健康和生态环境安全，因此，构建灵敏、高效的光电化学传感器用于检测环境微污染物具有重要意义。MOFs材料具有组成结构可调、性质可控、功能可设计的优势，本项目拟通过有机配体功能化、表面修饰改性、半导体多级敏化及电子传输介质杂化等手段调控其能带结构和电子传导性能，制备性能优异的MOFs光电功能材料，并将其作为传感器信号传导基质材料；分析目标检测物特性，结合分子印迹技术、免疫分析技术、适配体分析技术及酶标记手段等设计特异性传感识别模式，开发高灵敏度、高特异性、简单操作的环境微污染物光电化学传感器；系统研究基质材料组成、结构和传感识别模式对光电转化效率和光电催化性能的影响，阐明传感器响应机理。本项目研究有望为功能化MOFs的设计制备，光电化学传感器的发展进步，环境微污染物的快速检测做出积极的贡献。

新兴环境微污染物在环境介质中长期存在，对人类健康和生态安全造成严重危害，开发高灵敏、快速检测雌激素、抗生素等环境微污染物的光电化学传感器在环境检测研究领域具有重要意义。本项目致力于设计制备MOFs基光电功能材料用于环境微污染物的光电化学传感检测研究。由于MOFs材料具有组成结构可调、性质可控、功能可设计的优势，课题组通过调控MOF(Zr)、MOF(In)、MOF(Ti)等MOFs材料的能级结构、光吸收性能和电子传导机制，设计制备了一系列MOFs基复合材料，通过物相结构和光电性能表征证明了采用有机配体功能化、表面修饰改性、半导体多级敏化、电子传输介质杂化等手段能促进光生载流子快速迁移和有效分离，提高修饰电极的光电响应和光电转换效率；本项目以典型环境激素和抗生素为目标检测物，结合氧化还原反应、免疫分析、适配体分析等手段设计特异性传感识别模式，成功构建了一系列无标记型、竞争型和免疫型光电化学传感器，实现了对四环素、己烯雌酚、雌二醇的快速、灵敏检测，结果表明MOFs材料大比表面积及规则孔道结构增加了电极表面活性位点，实现检测物的选择性富集，能显著提高传感器的稳定性、灵敏度和准确性。通过对基底材料信号响应机制和目标检测物传感识别模式研究，系统分析了光电转换功能材料结构、组成、形貌、表/界面性质等物性因素与传感器光电信号转换效率和目标检测物识别和检测灵敏度的关系；归纳总结了MOFs材料表/界面性质、光电转换和载流子分离效率与传感器性能间的一般规律。同时，本项目研究拓展合成了多种新颖的可见光催化材料和MOFs基电致发光材料，用于环境污染物的催化降解和肿瘤标志物的电致化学发光传感检测研究。本项目研究工作已在Biosensors and Bioelectronics、ACS Applied Materials & Interfaces、Sensors and Actuators B: Chemical、Applied Catalysis B: Environmental、Journal of Hazardous Materials等国际学术期刊上发表SCI收录论文10余篇，申请国家发明专利8项，相关研究成果获全国商业联合会科学技术一等奖1项。本项目研究成果在新型光电功能材料开发、化学传感技术发展以及环境介质中微污染物检测等方面具有十分重要的意义。