【作者】 陶金龙；

【导师】 徐蔚青； 徐抒平；

【作者基本信息】 吉林大学 ， 物理化学， 2012， 博士

【摘要】 贵金属纳米粒子独特的光学性质-局域表面等离子共振(Localized SurfacePlasmon Resonance, LSPR)明显依赖于粒子的组成、形状、尺寸和周围环境，已经在表面增强光谱学、光电器件以及生物医药等诸多领域被广泛应用。因此，有效地调控贵金属纳米粒子LSPR(形貌和尺寸等)对与之相关的诸多研究和应用是十分必要的。本论文围绕金银纳米粒子的合成及其在表面增强拉曼散射(SurfaceEnhanced Raman Scattering, SERS)和织物染色中的应用，主要研究内容如下：1．探讨温度在光诱导合成各向异性银纳米粒子过程中作用。借助自行搭建可控温的光诱导装置，研究了温度对光化学反应的影响。利用消光光谱监测不同温度（10-90℃）下光诱导制备各向异性银纳米粒子的过程，采用透射电子显微镜对粒子形貌进行表征，探讨热效应对光诱导反应的影响。2．快速合成各向异性金纳米粒子，并研究其在SERS光谱中的应用。发展了一种室温下快速简便地合成从纳米枝状到微米板状金纳米粒子的湿化学方法。合成过程中没有额外引入稳定剂和结构导向剂，通过调节还原剂（香豆素480）和前驱体（氯金酸）的比例可以合成出不同形状和尺寸的金纳米粒子。以巯基吡啶(4-MPY)为探针分子对得到的金纳米粒子的SERS活性进行了评估。3．比较两种不同形状盘状银粒子膜的SERS活性。在石英基片上组装的三角形银纳米粒子被原位转化为圆盘状粒子。以不同形状自组装的银纳米粒子膜为SERS基底，研究了与LSPR相关的SERS增强。在不同激发波长的激发下，比较了两种粒子组装膜的SERS光谱差异。当SERS基底的表面等离子体共振(Surface Plasmon Resonance, SPR)吸收带与激发波长重叠较多时，该基底的SERS信号被极大地增强。4．通过加热和光诱导方法合成羟基羧酸盐稳定的金纳米粒子，并将其应用在织物和纤维的染色中。对比研究了三种羟基羧酸盐柠檬酸钠、苹果酸钠和酒石酸钠在加热和光诱导合成金纳米粒子的过程的作用。详细讨论了稳定剂和反应条件对金纳米粒子LSPR性质的影响。在一定的pH下，将得到的不同稳定剂包覆的、具有鲜艳颜色的金纳米粒子用于织物、纤维的染色，染色后的织物和纤维由于金纳米粒子的LSPR性质而表现出不同的颜色。更多还原

【Abstract】 Localized Surface Plasmon Resonance (LSPR) is the unique optical character of noblenanoparticles (NPs). The LSPR of noble nanoparticles mainly depend on thecomposition, shape, size and surrounding environment. Among all the strategy tofabricate noble NPs, Photo-induced method is considered to be an effective strategy toproduce anisotropic metal NPs. The thermal effect in a photo-induced process isderived from light. To learn about the effect of temperature in a photo-inducedreaction is of importance for obtaining uniform and mono-disperse NPs. In addition tophoto-induced reaction, wet chemical method is also a popular way to synthesizemetal NPs. However, developing simple and efficient methods remain a challenge.Surface Enhanced Raman Scattering (SERS) is one application of noble NPs,however, SERS enhancement of anisotropic metal nanoparticles depends on manyfactors, including shape, size and aggregation extent, which are complex andentangled in most cases. To fairly compare difference in enhancement ability andgetting rid of interlacement of other factors, it is significant to develop a simplestrategy to probe the SERS properties of metal nanoparticles. The stabilizer play animportant role in the synthesis and application of metal NPs. Hydroxy carboxylate,citrate, malate and tartrate are nontoxic reagents and gold NPs stabilized by all aboveprove better biocompatible, which facilitates the application of metal NPs. Based onabove view, the thesis is outlined as follows:1. The role of temperature in synthesizing anisotropic silver nanoparticlesby photoinduced method.Exploring the themal and light effects in photo-induced reaction is important forfurther developing photo-induced method. Products of a photo-induced reactionstrongly depend on many factors, including the intensity and wavelength of lights, the pH and temperature and so on. We systematically investigated the effect oftemperature on photochemical reaction, which was carried out by a home-madedevice at exact temperatures. Extinction spectroscopy was used to monitor thephotochemical reaction process of synthesizing silver NPs at different temperature(10-90℃). The morphologies of resulant silver nanoparticles were characterized bytransmission electron microscopy (TEM). The results showed that the temperatureplayed an important role in the particle growth, the shape/size control and the stabilityin a photochemical reaction; the main product is nanoprisms with much faster growthrate and better stability at90℃.2. Fast synthesis of gold nanoparticles with different shape and theirapplications in SERS.A fast and easy method to synthesize gold NPs was developed by wet chemicalmethod at room temperature, resulting in dendritic and discal nanoparticles withnanometers to microns in size. Gold NPs with different sizes and shapes can beprepared by adjusting the ratio between the reducer (Coumarin480) and the precursor(HAucl4). Fixing chloroauric acid concentration (9.8×10-5M) and the reducing agentis increased, the as-prepared particles are similar to spherical, however, increasing theconcentration of chloroauric acid continuously to2.94×10-4, discal NPs are obtainedand the particle size became smaller. In contrast, increasing the amount of chloroauricacid, the main product is dendritic NPs. By comparing SERS intensity of the threedifferent shaped gold nanoparticles, we find the dendritic structure displayed thestrongest enhancement to4-MPY.3. Comparison of Surface-Enhanced Ramans scattering spectra on twokinds of silver nanoplate films.The shape of noble metal NPs has great impact on SERS Substrates. Weexplored the relationship between LSPR and SERS activity of assembled silver filmwith different shape. Shape conversion from silver nanoprisms to nanodisks on slideswas in situ carried out by heating. SERS spectra on silver nanoprisms and nanodiskswere compared under different excitation lines and the difference in SERS intensitieswas discussed. It is demonstrated that SERS signals were greatly enhanced when theSPR band of a SERS substrate overlapped with the wavelength of excitation laser; theEM mechanism dominated SERS enhancement. The observation about therelationship of LSPR and SERS enhancement is in favor of further development of SERS mechanism and fabrication of optimal SERS substrates.4. Using hydroxy carboxylate to synthesize gold nanoparticles in heating andphotochemical reactions and their application in textile colouration.Citrate, malate and tartrate can be used to synthesize gold NPs using heating andphotochemical methods. NPs synthesized by the heating method from citrate weremore uniform than those from malate and tartrate by the same method. The formationrates of gold NPs by heating were influenced considerably by the pH of solutions; therate increased with a decrease of pH. NPs from photochemical synthesis were eggshaped and non-uniform regardless of the ligand used. The colour of the NPs may betuned by particle size, which is affected by ligand and synthesis method. Gold NPscan be used to colour wool fabric, silk and nylon fibres using conventional exhaustdyeing from a slightly acidic bath.更多还原