以硒、钴、硅和锡等纳米粒子为模板，研制粒径可控、壳厚及组成可调、表面结构规整的过渡金属一元及多元合金或双壳空心球状纳米粒子及其修饰电极，以吡啶、一氧化碳和有机小分子为探针，开展电化学原位表面增强拉曼光谱研究，利用各种先进的纳米材料表征技术探讨一元及多元过渡金属空心球状纳米粒子的合成机理，创立、发展并完善制备系列过渡金属空心球状纳米粒子的新方法；考察一元及多元过渡金属空心球状纳米粒子种类、组成、粒径、壳厚、表面形貌、结构及在玻碳、硅片和铂等基底电极上构建、组装修饰电极的方法、工艺和修饰电极表面状态对有机小分子电催化活性和SERS效应的影响。为研制SERS效应强，对有机小分子电催化活性高的直接燃料电池阳极,拓展SERS技术的使用范围，深入开展SERS机理的研究提供实验与理论依据。

Two challenges have to solve in the in-situ SERS investigation of the electrocatalytic oxidation of C1 molecule. Firstly, the SERS activity of Pt group metals that show good catalytic oxidation activity towards C1 molecules is too weak to meet the requirement of the in situ Raman characterization of the electrocatalytic oxidation behavior of the C1 molecules. Secondly, the electrocatalytic activity and the price of Pt groups metals and their alloys is still far from satisfactory, which requires discovery of new catalytic materials. Therefore, the attempt to pursue material with a high SERS activity and a good electrocatalytic activity has never been given up. The present project is to prepare Au core and Pt shell nanoparticles and the modified Pt or GC electrodes and uses them for the electrocatalytic oxidation of C1 molecules investigated by electrochemical method and in situ SERS technique. Selenium nanoparticles were used as the template for synthesizing Pt, Au, Pt-Au hollow nanoparticles with a controllable diameter and shell thickness. Several characterization techniques for nanomaterials were used to characterize the morphology, composition, structure and properties of the synthesized nanoparticles. The SERS and electrochemical properties of these nanoparticles-assembled electrodes were investigated using pyridine, thiocyanide, and C1 molecules as the probe molecules. The effect of the composition, size, shell thickness, surface morphology and structure on the electrocatalytic activity over C1 molecules was systematically analyzed. We have made meaningful effort to achieve anodic materials with good electrocatalytic activity and stability and to extend the application of the SERS technique.

开展C1分子电催化氧化行为的原位SERS研究需要解决两大难题：一是增强对C1分子氧化有催化活性的Pt等过渡金属电极的SERS信号；二是提高Pt等过渡金属及其合金电极对C1分子氧化的电催化性能。因此，人们一直尝试研制SERS效应强，对C1分子电催化氧化性能好的催化材料。本项目在研制核壳结构的Pt包Au纳米粒子及其修饰Pt（Gc）电极[Aucore@Ptshell/Pt（Gc）]，开展对C1分子电氧化和原位SERS研究的基础上，进行了过渡金属纳米空球修饰电极的电化学和拉曼光谱研究。以硒球为模板合成了粒径可控（60-120nm），壳厚可调（5-25nm）的Pt、Au、Pt-Au等过渡金属纳米空球及其修饰电极，以吡啶、硫氰根和C1分子为探针，开展了常规电化学和电化学原位SERS研究。利用多种纳米材料检测技术，表征了所合成的纳米空球的表面形貌、组成、结构和性能 ，发展了制备过渡金属纳米空球的方法；分析了过渡金属纳米空球的组成、粒径、壳厚、表面形貌和结构对C1分子电催化氧化性能的影响。为研制对C1分子电催化活性高、稳定性好的直接燃料电池阳极和拓展SERS技术的应用范围进行了有益的探索。