基于MOFs构效调控的高灵敏选择性电化学传感机理与方法研究

This project aims to develop novel electrochemical sensing materials with excellent properties, and to construct highly sensitive and selective electrochemical determination system. A series of metal-organic frameworks (MOFs) were prepared and their electrochemical properties were tuned through changing the electron shell structure of metal ions as well as the sort and number of the function groups of ligands. The influences of metal ions and ligands of MOFs on the morphology, structure, electrocatalytic ability, selective recognization ability and interface enhancement ability were deeply investigated, and consequently the structure-activity relationship were elucidated. After that, the catalytic enhancement and selective recognization mechanisms of univariate and multivariate MOFs toward the targets that is closely related to human health were studied. The mechanisms for the remarkable improvement of sensitivity and selectivity of electrochemical detection were explained. As a result, highly sensitive and selective electrochemical determination methods were developed, and then used in practical sample analysis. . This work will open a new thought for the preparation of highly sensitive and selective electrochemical sensing materials. It will also provide new methods for the rapid detection of trace environmental pollutants and neurotransmitters. This work is quite important from the points of theory and application. Meanwhile, the obtained catalytic enhancement and selective recognization mechanisms are helpful to construct superior electrochemical sensing systems.

为研发性能优异的新型电化学传感材料，构建高灵敏度、高选择性的电化学检测新体系，课题拟通过调节金属离子的电子层结构以及配体官能团的种类和数量来调控金属有机框架材料（MOFs）的电化学性能，深入研究金属离子和配体种类对MOFs材料的形貌结构、电催化能力、选择性传质识别能力以及界面增强能力的影响规律，阐述二者的构效关系；在此基础上，研究所制备的单组分、多组分MOFs敏感材料对一些与人体健康密切相关的靶标分子的催化增敏和选择性识别机制，阐述显著提高电化学检测灵敏度和选择性的作用机理，建立高灵敏度、高选择性的电化学检测新方法，用于实际样品分析。. 课题将为高灵敏度、高选择性电化学传感材料的研制开创一条新思路，并为痕量环境毒物和神经递质等的快速检测提供新方法，具有重要的理论和现实意义。此外，课题所获得的催化增敏和选择性识别机理有利于构建更优秀的电化学传感体系。

围绕MOFs的形貌调控制备、催化增敏机制及传感应用开展了系统的研究，探究了配体类型、金属种类、制备条件的影响，获得了MOFs显著提高电化学检测灵敏度和选择性的作用机理，建立了污染物、食品有害成分、神经递质等的高灵敏度、高选择性、快速的电化学测量新方法；用于实际样品分析，结果准确。发表通讯作者论文23篇，圆满完成了各项任务。主要成果如下：.配体调控Cu-MOFs的电催化传感活性及分析应用。以Cu2+为中心，不同有机羧酸为配体，通过阴极还原在电极表面原位制备出不同的Cu-MOFs。发现配体对Cu-MOFs的形貌、铜活性位点数、电催化活性、响应面积以及信号增强能力有显著影响。DFT计算和RDE实验表明，不同配体的Cu-MOFs对H2O2的结合能、还原催化活性以及信号增强效应不同， H3BTC制备的Cu-BTC性能更优。该研究表明通过改变配体可以调控Cu-MOFs的催化能力和传感灵敏度与选择性。成果发表在Adv. Func. Mater.等期刊上。.还原电位调控Cu-BTC的催化增敏机制及传感应用。发现不同电位制备的Cu-BTC对NADH的催化氧化活性不同，同时对生物小分子、环境雌激素和偶氮染料的信号增强能力也有较大差异。这说明还原电位可以调控Cu-BTC的形貌、催化能力及传感性能。成果发表在J. Phys. Chem. C、Sensor. Actuat. B-Chem.等期刊上。.基于石墨烯与Cu-MOFs协同增敏的高灵敏电化学传感策略。在石墨烯表面原位复合Cu-MOFs，二者复合后有很强的协同催化增敏效应，为构建高灵敏度电化学传感体系提供了一种新策略。成果发表在Anal. Chem.、Carbon等期刊上。.金属中心调控MOFs的增敏机制及分析应用。发现不同金属中心对M-BTC的形貌、响应面积、电子交换速率和富集能力有显著影响，进而影响电化学传感的灵敏度与选择性。成果发表在Anal. Chim. Acta、Sensors and Actuators B 等期刊上。.基于剥离石墨烯形貌缺陷调控的电化学传感及应用。研究了球磨时间、插层分子、离心速度等对剥离石墨烯的形貌、片层大小、缺陷水平和氧含量的影响，阐述了形貌缺陷与传感灵敏度间的构效关系，建立了环境污染物、神经递质的高灵敏检测新方法。成果发表在Small、Carbon、J. Hazard. Mater.等期刊上。