金、钯纳米粒子气液界面组装新方法与应用-物理化学专业论文.docxVIP

膜，研究了其成膜机理，考察了组装膜的表面增强拉曼散射效应和／ 膜，研究了其成膜机理，考察了组装膜的表面增强拉曼散射效应和／ 或电催化活性。主要内容如下： 1．酸性介质中，用过量亚锡还原氯金酸，得到以亚锡(SnCIs- 形式)为保护剂的稳定金溶胶，该溶胶可在隔绝空气的条件下保存数 月之久。但在与空气接触下陈化溶胶，则可在短时间内于气一液界面 得到金纳米粒子组装而成的多孔结构超薄膜。拉曼光谱等实验证明， 该界面组装过程涉及空气中的氧所导致的配体交换。即空气中的氧气 氧化消耗溶液表面层的二价锡(Sn(II))，引起溶液表面层的金纳米粒 子发生SnCl3和Cl‘之间的配体取代，Cl。取代SnCl3配体后，溶胶表面 层中的金纳米粒子失稳，在气．液界面上自发组装成膜。另外，结合 密度泛函理论(DFT)计算，对该配体变换机理进行了解释。 2．该金纳米粒子组装薄膜表现出良好的SERS效应和电催化活 r‘r 性。以该组装膜为SERS基底，测定了吡啶、邻菲罗啉、烟酰胺的SERS i 光谱。另外，该组装膜在碱性溶液中对乙醇、葡萄糖、维生素C的电氧化有较好的催化活性。 光谱。另外，该组装膜在碱性溶液中对乙醇、葡萄糖、维生素C的电 氧化有较好的催化活性。 3．酸性介质中，过量的Sn(II)JJH热还原氯化钯得到稳定的钯溶胶， 持续加热陈化一定时间后，可在气一液界面获得Pd纳米粒子的组装膜。 其机理可能涉及加热条件下Pd纳米粒子往气一液界面上的扩散与组 装。将Pd纳米粒子组装成的超薄膜修饰在玻碳电极或光亮Pd电极上， 在碱性条件下对乙醇和甲酸的电催化氧化表现出较好活性。 关键词：金；钯；纳米粒子；界面；组装；表面增强拉曼光谱；电催 化氧化 lL■■r} lL■■r } New methods on the assembly of nanoparticulate gold and palladium at the water-air interface and their applications AB STRACT Nanopartices(NPs)and their assembly films of noble metals like gold and palladium have attracted a great deal of attention due to their broad application in such areas as optics，nanoelectronics，sensing， catalysis，and SO forth．In recent years lots of efforts have being made to the preparation of noble metal NPs and their assembly at the interfaces of gas-liquid，liquid-liquid．Therefore it is of great significance to develop new interracial assembly methods on fabricating two— and three—dimensional functional films of noble metal NPs．In this thesis，we prepared colloidal gold and palladium with excessive divalent tin Sn(II) as both reductant and capping agent，made assembly films of the two kinds of NPs at the air-water interface，studied the assembly mechanisms， and showed the applications of the assembled films in surface．enhanced Raman scattering(SERS)and／or electrocatalysis．The main contents are summarized as follows： 1．A gold colloid Was synthesized by the reduction of AuCl4‘with excessive divalent tin Sn(II)in an acid medium，which was stable for months under airproof condition by the protection of Sn(II)C13一．However, ultra