Interfacial Assembly and Preparation of Novel Nanostructures & Electrochemical Surface Plasmon Resonance Studies

围绕论文题目“纳米结构界面组装及电化学SPR研究”，我们将SPR与电化学技术有机的结合起来，建立了电化学SPR（EC-SPR）技术，开展了相关的EC-SPR研究工作。同时，在一些特殊纳米结构的界面组装方面进行了创新研究。本论文研究工作的主要内容和创新点表现在以下几个方面：1．首次成功地将纳米粒子自组装膜模板与化学镀金技术相结合成功地用于湿化学法制备SPR响应基片，攻克国际上仅用物理法制备SPR镀金片的局限和困难，为SPR技术的进一步普及奠定了一定的基础。2．此外，还成功地将纳米粒子自组装膜模板与化学镀金技术相结合，制备了Au（III）单晶纳米岛阵列薄膜及电极。3．在国内率先将电化学和表面等离子体共振（SPR）光谱技术相结合，构建了EC-SPR仪器操作系统；并将此技术用于现场原位表征和研究导电聚合物薄膜和生物大分子（DNA和电活性蛋白质分子）纳米结构组装体的光电特性。4. 首次合成并报道了纳米粒子模板法制备中空的银／金表面钉状双金属纳米粒子，及其在水和空气界面受扩散受限聚集控制的二维介观分形聚集。丰富和拓展了纳米粒子二维分形聚集的研究。5．将欠电位沉积电化学方法拓展用于表面微加工。实验结果表明，对化学镀制备的多晶金SPR响应基片进行连续的银欠电位沉积与溶出电化学处理，不仅可以改善金膜表面的粗糙度，还能对表面的原子进行结构重排，使其具有An（III）的电化学响应特征；SPR信号对SPR响应金膜表面的原子排列非常灵敏。6．将欠电位沉积电化学法用于新颖的纳米催化剂设计，首次制备了铂原子单层沉积的纳米金单层膜并成功地用于4电子氧催化还原反应。大基于纳米受限环境下水的特殊性质（不挥发性）的启示，成功地进行了DDAB表面活性剂泡囊和环状多金属氧酸盐（POM）纳米簇的仿生超分子模板界面静电组装。Both interfacial assembly and preparation of nanostructures and electrochemical surface plasmon resonance studies are active and promising in the chemistry of materials and analytical chemistry fields. We combined SPR with electrochemical method to carry out several EC-SPR studies. On the other hand, we designed and prepared some novel nanostructures on templates surface. We obtained some new results in following aspects: 1. We have developed a new and alternative approach for preparing SPR-active gold substrates. Our strategy is based on self-assembly of gold colloid monolayer and followed by electroless gold plating. The method affords facile control of both the thickness and the surface roughness of the resulting gold films on the nanometer scale, and the as-prepared substrates are more suitable for electrochemical studies. 2.A new and simple approach for preparation of Au(111) single-crystal nanoisland-array electrode ensembles, based on fine colloidal Aumonolayer-directed seeding growth, has been reported. 3. The alternate polyion L-by-L growth method was successfully used to construct films containing CT ds-DNA and Mb on cysteamine-modified gold electrode. The formation of L-by-L (DNA/Mb)n films was confirmed by both in-situ SPR monitoring and cyclic voltammetry. (DNA/Mb)_n films gave stable, quasi-reversible voltammetric peaks involving the Mb heme Fe~(III)/Fe~(II) redox couples of the proteins. 4. One-pot preparation of shell-type silver-gold bimetallic nanostructures with hollow interiors and bearing nano-spikes, based on colloid seed-engaged replacement reaction and colloid-mediated deposition reactions, has been reported. We also report firstly on a genuinely aggregation-based strategy to prepare mesoscopic, two-dimensional fractal aggregates (even thin films) of bare (without adsorbate) silver/gold (Ag/Au) roughened sheil-type nanoparticles via diffusion-limited aggregation (DLA) at the air/water interface, and demonstrate that control over the concentration of plating solution can not only be used to fine-tune the resulting fractal patterns, but also drastically affect crystal growth of particles. 5. Silver underpotential deposition (UPD)-induced surface atomic rearrange ment of polycrystalline gold nanofilms was probed using surface plasmon resonance spectroscopy (SPRs) as a novel probe tool in combination with1 cyclic voltammetry. Interestingly, upon repetitive electrochemical UPD and stripping of Ag, the surface structure of the resulting bare Au film is rearranged, which causes a large angle shift of SPR R- 0 curves to a lower SPR angle. Some surface atomic rearrangement can cause a pronounced SPR angle shift. 6. We presented a novel electrochemical strategy to nanoparticle-based catalyst design using the underpotential deposition (UPD) redox replacement technique. The as-prepared ultrathin Pt-coated Au nanoparticle monolayer electrodes reduce O_2 predominantly by four electrons to H_2O, as confirmed by the rotating ring-disk electrode (RRDE) technique. 7. Inspired by unique properties of nano-confined water, we reported that the ring-shaped polyoxomolybdate (POM) nanoparticles can self-assembly onto the cationic DDAB vesicle surfaces through coulomb interactions, and form robust, structurally well-defined core-shell supramolecular assemblies