多功能蛋黄－蛋壳结构聚苯胺负载型贵金属纳米催化剂的合成及性能研究

The former project has discovered novel strategies for high performance conducting polymer-supported noble metal nanocatalysts, has established redox mechanisms and morphology control rules involved in conducting polymer-supported noble metal nanocatalysts, and has revealed relationships between structure and property of conducting polymer-supported noble metal nanocatalysts. However, in order to realize long life together with high performance conducting polymer-supported noble metal nanocatalysts, strategies must be developed to control over catalyst size and overcome aggregation and leaching of noble metal nanocatalysts. Based on previous observations, yolk/shell structures are further introduced to develop multifunctional yolk/shell nanostructures of magnetic PANI-supported noble metal nanocatalysts. The mesoporous structures of SiO2 shells with nanochannels allow molecules to diffusion inside and outside, whereas the voids between silica shells and noble metal catalysts provide ideal room for inclusion of sufficient molecules with efficient contact with catalysts. Catalytic performances of yolk/shell nanostructures of magnetic PANI-supported noble metal nanocatalysts in selective oxidation of alcohols, Suzuki-Miyaura cross-coupling reactions are then investigated. According to experimental results, relationships between structure and property will be revealed and summarized, which are believed to be instructive for application of conducting polymer in domain of nanocatalysts, and design of novel and efficient functional noble metal nanocatalysts.

青年科学基金紧密围绕项目目标，建立了高性能导电高分子负载型贵金属纳米催化剂构筑新方法，阐明导电高分子负载型贵金属纳米催化剂的反应机制及调控规律，揭示了催化剂结构与性能之间的关联。然而，要真正得到长使用寿命高活性多功能聚苯胺负载贵金属纳米催化剂，必须寻求行之有效的贵金属纳米催化剂粒径控制新途径以及解决纳米催化剂重复使用过程中催化剂纳米粒子的团聚及流失问题。在前期研究基础之上，进一步引入蛋黄－蛋壳结构，拟构筑多功能蛋黄－蛋壳结构磁性聚苯胺负载型贵金属纳米催化剂，介孔二氧化硅外壳提供分子通道，纳米空间的存在有利于反应分子与催化剂的充分接触从而增加催化效率。研究蛋黄－蛋壳结构磁性聚苯胺负载贵金属纳米催化剂在醇选择性氧化、Suzuki-Miyaura偶联等重要有机反应中的催化特性，揭示构效关系，为拓展导电高分子在贵金属纳米催化剂领域的应用提供理论基础，并发展新型、高效功能性贵金属纳米催化剂。

负载型贵金属纳米催化剂体系的构筑及催化性能研究是纳米催化领域的热点。要真正得到长使用寿命的高活性负载贵金属纳米催化剂，必须寻求行之有效的贵金属纳米催化剂粒径控制新途径以及解决纳米催化剂重复使用过程中催化剂纳米粒子的团聚及流失问题。将蛋黄-蛋壳结构引入到磁性聚苯胺负载贵金属纳米催化剂中，从而构筑新型蛋黄-蛋壳结构磁性聚苯胺负载贵金属纳米催化剂体系，介孔壳层可以有效控制贵金属催化剂的粒径并赋予其高稳定性，同时磁性材料的引入赋予其简便易行的磁性分离特性，是具有重要理论意义和潜在应用价值的研究课题。.本项目按照既定目标，成功构建了蛋黄/蛋壳结构导电高分子负载型纳米催化剂，并实现磁性功能的引入以及阐明了构效关系。如四氧化三铁@聚苯胺@金/介孔二氧化硅蛋黄-蛋壳结构纳米催化剂，金/聚苯胺蛋黄/蛋壳结构纳米催化剂等。此外，在导电高分子负载型蛋黄/蛋壳结构功能复合纳米催化剂的结构调控基础之上，在材料组成的多样性和功能性方面进行了拓展和衍生，进一步引入石墨烯、金属氧化物（氧化钛、氧化锰、氧化镍等）材料，根据复合材料的功能特性，应用方面拓宽至染料降解和光解水制氢光催化、氧还原电催化、超电容材料等环境和能源方面。在本项目资助下，在Chemical Communications, Langmuir, Journal of Materials Chemistry A等化学及材料类学术期刊发表SCI论文23篇，其中4篇论文分别被Chemical Communications, Soft Matter, Journal of Materials Chemistry A学术期刊选为当期封面文章。申请国家发明专利3项，已获授权国家发明专利2项。已培养硕士7名。研究生相关研究成果为拓展导电高分子在贵金属纳米催化剂领域的应用提供理论基础，并发展新型、高效功能性贵金属纳米催化剂。