基于仿生原理和超分子组装设计制备高性能有机分子-石墨烯复合气敏材料

Design and preparation of high performance gas sensing materials have been highly significant in many fields, such as life-supporting in air and space, detection of toxic gases in industry, discovery of leakage of natural gas in daily living and military equipment. In this proposal, based on our previous works and also inspired from the structure and functional mechanism of high performance gas sensing systems in nature, we propose to prepare three systems of graphene-based gas sensing materials. (1) Mimicking the multi-level and folded structure of nerve cell network in canine nose, we propose to prepare a NO2 gas sensing composite through supramolecular assembly of organic moleucles, graphene and metalic nanoparticles. (2) Learning from the reversible reaction of biologic carbon anhydride enzyme (CA) with CO2, small molecules and block copolymer containing amidine groups and aromatic perylene rings are designed in this proposal and utilized to be supramolecularly assembled with graphene via π-π stacking interaction to provide a unique CO2 sensing materials. (3) With the similar structure to the capillary vessel and alveolus, polyelectrolyte-modified graphene based nanoscrolls and micrometer size hollow spheres are prepared for NO2 sensing, respectively. On the basis of fundamental research, our work is going to focus on the relationship between microstructures and gas sensitivities of the three systems of graphene-based gas sensing materials, along with the interaction mechanism among molecules of gas and composite materials. Further, the gas sensing mechanism will be ultimately explored, which is expected to be certainly beneficial for preparation and application of novel graphene-based gas sensing material which has outstanding gas sensitivity, high gas selectivity and good stability.

设计制备高性能气敏材料在航空航天、工业生产、民用生活和国防军用等方面都具有极其重要的意义。本项目中，在前期工作基础上，我们受自然界中高性能气体响应体系结构和相关功能原理启发，拟运用功能有机小分子和高分子与石墨烯进行超分子组装，仿生制备三种石墨烯基气敏材料：（1）模拟狗鼻中的神经元网络多级褶皱结构制备有机分子-石墨烯-金属纳米微粒复合NO2气敏材料；（2）模拟碳酸酐酶与CO2特异反应制备脒基小分子、高分子修饰的石墨烯基CO2气敏材料；（3）模拟毛细血管和肺泡结构制备聚电解质-石墨烯复合纳米管和空心微球NO2气敏材料。拟从基础研究的角度出发，重点对获得的三类石墨烯基气敏材料微观结构与宏观气体传感性质间的联系、复合材料与气体分子间的选择性相互作用机理等规律性问题进行分析和总结，探求材料的气体传感机制，为制备高灵敏度、高选择性和高稳定石墨烯基气敏材料及其应用提供理论和实验依据。

本项目按原项目书方案完成了具有仿生结构的石墨烯基气体传感材料的设计，成功制备并研究了三维褶皱石墨烯基NO2纳米片材料，石墨烯基纳米卷NO2传感材料，以及石墨烯基空心微球气体传感材料。此外，我们利用不同客体修饰石墨烯制备了多种高性能室温气体传感材料：D-π-A结构偶极分子修饰的石墨烯基气体传感材料，偶极分子/金属离子共同修饰的石墨烯基气体传感材料，偶极分子和ZnO纳米颗粒修饰的石墨烯基室温甲醛传感材料，具有氧化还原性质的染料分子修饰的石墨烯基NO2传感材料，聚苯胺包覆的3D中空石墨烯微球氨气传感材料等。针对实际应用，我们对传感器器件进行了优化研究，主要集中在打印电极宽度对电极气敏性能影响的研究，以及基于丝网印刷工艺制备透明传感材料及器件的研究。通过本项目执行，培养了博士生3名，硕士生19名，以第一作者或者通讯作者发表SCI论文14篇，申请专利7件，已授权2件，获批国家自然科学基金面上项目1项，省部级项目3项。本项目研究成果为制备高性能石墨烯基复合气体传感材料及器件提供了有力的理论指导和实验依据。顺利实现了本项目的预期目标并超额完成了项目预期任务。