沸石咪唑型MOFs/贵金属纳米粒子复合物的结构调控及对食品有害物的响应机制

The problem of food safety is becoming more and more serious, and the rapid and sensitive detection method of harmful substances in food is urgently needed. Metal-organic frameworks (MOFs) possess the advantages of large surface areas and tunable pores, enabling them to be the potential electrochemical sensor modifiers. However, most MOFs belong to poor electrical conductors, the disadvantage of MOFs limit their wide application in sensors. In this proposal we will adulterate the conductive materials with the MOFs due to their high conductivity in the fabrication of sensors. The nanoscale MOFs will be synthesis to improve active area of MOFs and loading capacity of metal nanoparticles (MNPs). The small size of MNPs inserted into MOFs or surface will be investigated, the synergistic effect between MNPs and MOFs effectively integrates their respective multiple advantages, resulting in a much enhanced catalytic performance. The preparation of the sensor with the composites will be studied for the detection of food harmful substances (hormones, additives and antibiotics), the new interface for sensing harmful substances in food will be established. The reaction mechanisms of the harmful substances in food at sensors will be revealed in combination with theoretical calculation and in situ infrared spectroscopy. The result will provide guidance for the sensitive detection of other harmful substances in food.

食品安全问题日益严峻，迫切需要食品中有害物质快速灵敏的检测方法。金属有机骨架材料（MOFs）具有比表面积大，孔径可调等优越性能，适合作电极修饰材料，但其导电性差限制了其在电化学传感器方面的广泛应用。项目提出制备MOFs传感器时引入导电剂。通过调控沸石咪唑型金属有机骨架结构材料的尺寸和形貌，增加MOFs的比表面积和金属纳米粒子的负载量。通过将小尺寸的金属纳米粒子（MNPs）插入MOFs的空穴中或是负载于表面获得复合材料，调控MOFs/MNPs的结构利用二者之间的协同效应发挥复合物的催化活性，探索以该材料为电极修饰物的化学传感器的构筑。通过复合材料电化学传感器对食品中有害物质（激素、添加剂、抗生素）催化检测效果，搭建食品中有害物质的电化学传感新界面。通过理论计算和原位红外光谱技术，揭示食品中有害物质在电化学传感器上的电子转移机理和复合电极的催化本质，为食品中有害物质灵敏检测提供科学依据。

金属有机骨架材料（Metal-organic frameworks，MOFs）与贵金属纳米粒子以及碳基材料的复合表现出很多优异性能，尤其在电化学传感方面的研究正在兴起。研究工作围绕钴基金属有机骨架材料的形貌调控制备、催化增敏机制及传感应用开展了系统的研究，探究了制备条件、复合基底的影响，简捷高效制备一系列Co基、Ti基MOFs复合物及衍生物，包括ZIF-67与有序多孔碳、ZIF-67与碳纳米管，Ag-ZIF-67纳米羽片、Ag-CoNi-MOFs，Co纳米粒子和掺杂氮的碳纳米管复合物和Ti基MOFs衍生物等，构筑了显著提高电化学检测灵敏度和选择性的化学传感器，建立了污染物、食品有害成分、神经递质、中药有效成分等的高灵敏度、高选择性、快速的电化学测量新方法。揭示分析物在MOFs电化学传感器上的电子转移机理和催化本质，拓展了MOFs传感器在电化学领域的应用和发展。. 研究成果发表标注资金资助的学术论文14篇，成果发表在Journal of the Electrochemistry Society，Microchemical Journal，Rare Metals，Food Analytical Methods，Journal of Alloys and Compounds，International Journal of Hydrogen energy等期刊上，相关成果被Coordination Chemistry Reviews，Carbon，Microchimica Acta等期刊正面引用，产生了较好的学术影响，获得国家发明专利1项，出版学术专著《金属有机骨架(MOFs)构筑电分析传感器及应用》1部，培养了多名优秀的本科生，参加学术会议2次。