可用于便携式硝基芳烃类爆炸物电化学传感器的高灵敏纸电极的构筑及其性能研究

Nitroaromatic explosives are widely used in terrorist attacks, their accurate, rapid and trace detection has become an important issue of international concern. To fill the domestic blank in the field of portable electrochemical detection device for explosives, we propose a new idea for fabricating highly sensitive paper electrode based on the layer-by-layer assembly and synergistic sensitization of various nanomaterials. Here is our design strategy: 1) graphene-ionic liquid-carbon nanotube hybrid paper is prepared and employed as substrate； 2）polyaniline is decorated on the surface and layer gap of the paper by electropolymerization； 3）metallic nanoparticle catalyst is coated on the as-prepared composite materials by sputter coating, ultrasonication electrodeposition and dip-coating techniques. Finally, a hierarchical, flexible, freestanding metallic nanoparticle catalyst/polyaniline/graphene-ionic liquid-carbon nanotube hybrid paper is obtained. The composition and structure of each level of the paper electrode are optimized to explore the relationship between the micro/nano structure and the recognition effect. The performance of paper electrode for detection of different nitroaromatic explosives is investigated, which could be used for establishing sensitive and reliable electroanalytical method for explosives detection. We envision that this proposal will provide innovative method on the fabrication of high performance test strip for explosive detection, and lay a solid foundation for the research and development of portable electrochemical sensor for explosives, and also is of great significance for preventing and fighting against terrorism, as well as safeguarding world peace.

硝基芳烃类爆炸物在恐怖袭击活动中广泛使用，对其进行准确、快速、痕量的检测是国际上关注的重要问题。本课题针对国内便携式电化学爆炸物检测仪研究领域的空白，提出以多种纳米材料层层复合、协同增敏，构筑高灵敏爆炸物检测纸电极的全新思路。拟以石墨烯-离子液体-碳纳米管复合纸为基底，通过电聚合法负载聚苯胺，再利用溅射沉积、超声电沉积、浸渍拉膜等方法将纳米金属催化剂负载其上，从而制备具有多层次结构、柔性、无支撑的金属纳米催化剂/聚苯胺/石墨烯-离子液体-碳纳米管复合纸电极。优化各层面纳米材料的组成和结构，探讨微纳结构与识别效果之间的关系。考查复合纸电极对不同种类硝基芳烃的检测性能，建立灵敏、可靠的爆炸物检测分析方法。本研究为开发具有普适意义的高性能爆炸物检测试纸提供了创新方法，为研制新型爆炸物电化学传感器奠定了坚实基础，对预防和打击恐怖犯罪，维护世界和平意义重大。

硝基芳烃类爆炸物的准确、快速、痕量检测不仅对预防和打击恐怖犯罪意义重大，对监测和预防环境污染也至关重要。本项目以石墨烯、碳纳米管为基本构筑单元，通过离子液体进行表面修饰，以提高其可溶液操作性来制成浆料，利用真空抽滤法、溶液浇铸法和印刷法等制备了柔性自支撑纸电极。再通过超声电沉积法、浸渍拉膜法、原位化学还原法等将金属纳米粒子或金属氧化物负载其上协同增敏，制备了一系列不同结构和组成的纸电极，如：Pd纳米花/碳纳米管-石墨烯纳米片薄膜电极，聚苯胺/离子液体-碳纳米管-石墨烯复合纸，Pt纳米粒子/碳纳米管-MXene纸电极，PtPd合金/离子液体-石墨烯纸电极，纳米MnO2/离子液体-石墨烯纸电极，PtAu合金和Au纳米花/离子液体/石墨烯纸等，可用于硝基芳烃类爆炸物或其他小分子（H2O2，葡萄糖）的高灵敏电化学。其中，我们将Pd纳米花/碳纳米管-石墨烯修饰在丝网印刷电极上，与微型电化学工作站和平板电脑联用，开发了一款便携式爆炸物检测仪，对TNT的灵敏度为4.30 μA μM-1 cm-2，线性范围为0.2-100 μM，检测限为32.4 nM，对TNB的灵敏度为1.51 μA μM-1 cm-2，线性范围为0.1-100 μM，检测限为83.4 nM，可用于实际样品中微痕量硝基芳烃污染物的检测，相对标准偏差（RSD）小于5%，回收率（Recovery）大于95%。因此，本项目研发的石墨烯基柔性纸电极以及开发的便携式检测仪为微痕量的硝基芳烃类爆炸物的检测提供了一个全新的快速、准确、高效的方法，在国防和环境检测领域具有广泛的应用前景。