形貌调控纳米金属氧化物增敏机理及超灵敏食品安全分析新方法

Through chemical or electrochemical methods, nanostructured sensing materials of metal oxides with different shape and particle sizes were prepared. The influences of preparation parameters in their morphology were deeply examined. Consequently, the mechanism and technology were developed for the preparation of nanostructured electrode sensing materials with high surface area, high catalytic activity and strong accumulation ability. The electrochemical sensing properties of different-shaped metal oxides were investigated in detail to discover the intrinsic relationship between structure and activity. The interface physic and electrochemical scientific questions for the remarkable enhancement effects of metal oxides were resolved. As a result, the systematic and morphology-dependent electrochemical sensing theory for metal oxide nanoparticles was developed. After that, the electrochemical behavior, sensing and signal transfer mechanisms of highly toxic food additives/residues were studied on the surface of different-shaped metal oxide nanoparticles. Finally, novel theory and method were formed for highly sensitive, selecctive and rapid electrochemical detection of toxic food additives/residues, which was used in various food samples. From this work, we can acquire systematic theory on the prepartion of morphology-controlled sensing nanomaterials and the morphology-dependent electrochemical detection. The obtained sensing theory, sensing mechanism and preparation method are helpful to develop highly-sensitive and novel electrochemical sensing system. Meanwhile, this work will provide new method and new technology for the rapid and in-site food safety analysis. Therefore, it is quite important to guarantee "the safety on the tip of tongue of human being".

通过化学或电化学方法制备出不同形状、不同颗粒大小的纳米金属氧化物，探究制备参数对其形貌的影响规律，获得高比表面、高催化活性、高富集能力的纳米金属氧化物可控制备原理和技术。深入研究不同形貌纳米金属氧化物的电化学传感特性，阐述纳米构效关系，解决纳米金属氧化物显著改善电极响应性能的界面物理和电化学科学问题，建立纳米金属氧化物形貌电化学传感新理论。研究致癌性或高毒性食品添加物/残留物（如偶氮色素、抗生素、重金属等）在不同形貌纳米金属氧化物表面的电化学反应机理和信号增强机制，建立高灵敏度、高选择性、快速的电化学检测新理论和新方法，用于不同食品样品分析。 课题将在形貌可控纳米敏感材料的制备及形貌电化学传感检测方面获得系统性新理论，有利于构建更广泛的超灵敏纳米电化学检测新体系。同时，课题为食品安全的超灵敏快速检测提供新方法和新技术，对确保人民群众"舌尖上的安全"具有重要的现实意义。

围绕NMP剥离石墨烯、纳米FeOOH、多孔碳等敏感材料的形貌调控制备表征、增敏机制和传感应用开展了研究，获得了基于纳米形貌增敏显著提高电化学传感器灵敏度、选择性的界面作用机制，建立了有毒色素、环境污染物的高灵敏检测新方法，用于实际样品分析，结果准确；在Analytical Chemistry等SCI期刊上发表通讯作者论文18篇；圆满完成了各项研究任务。主要成果如下：.NMP剥离石墨烯的增敏机制及高灵敏电化学传感新方法。以NMP为溶剂，一步超声剥离制备出石墨烯纳米片，研究了剥离时间对其电化学性能的影响规律；发现剥离石墨烯的响应面积、电子交换能力以及对合成色素、环境激素的信号增强能力显著高于rGO和GO；探究了增敏机制，构建了一种广泛的、高灵敏的电化学传感平台；成果发表在Anal. Chim. Acta 825 (2014) 26（他引20次），J. Hazard. Mate. 283 (2015) 157（他引12次，ESI高被引）、Electrochim. Acta 115 (2014) 434（他引17次）。开展了NMP剥离石墨烯的电化学功能化研究，发现NMP剥离石墨烯经恒电位氧化后，电化学活性得到进一步改善，探究了电化学活化的增敏机制，构建了酚类物质高灵敏传感体系；成果发表在Anal. Chem. 87 (2015) 3294（他引20次）。.基于FeOOH形貌调控的高灵敏电化学传感新方法。开展了不同形貌纳米FeOOH的制备表征研究，阐述了形貌与其催化活性、界面增强效应之间的构效关系，建立了DES、BPA、4-CP等物质的电化学检测新方法，环境样品分析结果与HPLC一致；成果发表在J. Hazard. Mater. 307 (2016) 36、Electrochem. Commun. 68 (2016) 10。.多孔碳的形貌电化学增敏机制及传感应用。调节模板用量、模板大小实现了多孔碳的形貌调控，研究了形貌对电化学增敏效应的影响，构建了多种合成色素的高灵敏传感平台，食品样品分析结果与HPLC一致；成果发表Anal. Chim. Acta 887 (2015) 75。.Cu-BTC的电化学增敏机制及高灵敏传感方法。合成出Cu-BTC金属框架材料，研究了对合成色素、环境激素的信号增强机制，建立了高灵敏的检测新方法，实际样品分析结果准确。