多功能聚合物纳米纤维负载Pd单/双金属的可控构筑与电催化性能调控

How to control the precise microstructure and morphology of nanocatalysts by simple and uviversial methods is the main problem for the rapid development of nanocatalysts. The polymer/monometallic Pd and polymer/Pd-based bimetallic nano-catalysts suspension are prepared using multifunctional polymer, which are assisted by photothermal effect from radiation of visible light, as reductive, protective and directing agent in the presence of metallic precursor. The nucleation and controllable growth of nano-Pd metal and alloys are analyzed. Multifunctional polymeric nanofibers-supported monometallic Pd and Pd-based bimetallic nano-catalysts are prepared by electrospinning technology. The electrocatalytic performance of the catalyst modified glassy carbon electrode for small organic molecules oxidation is also investigated. The effects of microstructure, morphology, surface adsorbate of catalyst and electrospinning parameters on the electrocatalytic properties are studied deeply by structure characterization and performance tests. The controlled constructional conditions of Pd-based catalyst with different structures, sizes and morphologies are obtained by optimized experiments. By building the relations of microstructures of nanomaterials and electrocatalytic performance, the adjusting and tailoring of the electrocatalytic oxidation properties of organic small molecules were realized. The major object is not only to obtain a simple synthetic method for preparing nano Pd-based catalyst with controllable morphology and size，but to promote the catalytic properties to supply the fundamental and theoretical instructions for designing the industrial products.

如何以简易、普适的制备方法实现对纳米催化剂微结构和形貌的精确控制是纳米催化剂快速发展函待解决的主要问题。本项目在添加金属前躯体水相体系内，利用可见光源的光热效应，辅助以具有还原性、保护性和导向性等"多功能为一体"的聚合物为助剂，实现纳米金属及合金的成核和可控生长，得到聚合物/纳米金属催化剂复合基液。借助静电纺丝技术，利用聚合物的可成纤性制备纳米金属/聚合物复合纤维，采用电化学方法对有机小分子进行电催化氧化研究。通过结构表征和性能测试深入探索催化剂结构、形貌、分布状态、表面吸附物以及静电纺丝工艺参数等与电催化性能的关联效应，优化纳米Pd单/双金属催化剂的可控构筑条件，建立催化剂微结构与电催化性能之间的关系，实现对有机小分子电催化氧化性质进行裁剪和调整。预计该项目的研究不仅会开创一种负载型纳米催化剂的简易合成方法，而且会全面提升纳米材料的催化性能，为工业化产品设计和性能优化提供基础和理论指导。

紧密围绕项目研究目标，开创了系列制备高性能Pd基单/双金属和聚合物基贵金属等系列纳米催化剂的新方法，成功制备了一系列的纳米电催化剂材料，阐明了纳米电催化剂的合成反应机制及微结构调控规律，考察了纳米Pd基单/双金属材料和聚合物基纳米贵金属复合材料修饰电极对乙醇、甲醛、甲烷、络氨酸等有机小分子的电催化活性、抗中毒性和稳定性，阐明了聚合物基体与贵金属纳米粒子之间的相互作用，揭示了催化剂结构与性能之间的关系，实现了纳米材料的结构调整和性能调控；通过静电纺丝技术，简化实验工艺，获得尺寸均一、高比表面积和稳定的聚合物纳米纤维以及负载Pd的聚合物纳米纤维，系统研究了纺丝溶液的类型和浓度、溶剂类型、电压及接收距离等工艺参数对聚合物成纤性能的影响。通过本项目的开展，为拓展燃料电池用纳米电催化剂领域的应用提供理论基础，促进了电催化剂的商业化进程。在本基金的支持下，已在国内外核心期刊发表学术论文26篇，授权发明专利8项，受理发明专利4项。