中空银纳米球的制备及其性能研究

新型的金属纳米粒子因为独特的由表面等离子体共振诱导(SPR)的光学性质和很多的潜在应用而受到社会广泛的关注。在具有SPR效应的贵金属纳米粒子中,中空纳米结构有一个很高的散射系数,其共振频率通过改变中空核的尺寸和壳的厚度可以很容易地被控制。本论文中拟采用电化学方法结合电偶置换法在高定向热解石墨(HOPG)及金膜表面制备不同尺寸具有中空结构的银纳米阵列,研究了中空银纳米阵列的局域表面等离子效应(L-SPR),为其在SPR定性和定量研究中的应用提供理论指导。     

Laser synthesized nanoparticle alloys of metals with bulk miscibility gaps

The nanoscale alloying of metals with bulk miscibility gaps, Ag-Pt and Ag-Rh, has been investigated using pulsed laser ablation of solids in solution(PLASiS). The procedure was in two steps. In the first step, the suspensions of monometallic nanoparticles were prepared by ablation of a metal rod submerged in water. In the second step,the monometallic suspensions were mixed and alloying was induced by re-irradiation. For the Ag-Pt system, a surface plasmon resonance was observed in the monometallic silver suspension. The surface plasmon resonance vanished in re-irradiated Ag-Pt suspensions, indicating alloying. Selected Area Electron Diffraction(SAED)analysis showed that the nanoparticles had a fcc structure with a lattice constant intermediate between that of monometallic Ag and Pt nanoparticles. First principles theoretical investigations of the mixing energy of Ag-Pt clusters confirm that mixing is favored at around ～1 nm. The same procedure used for Ag-Pt was followed for Ag-Rh. In this system where the two metals present miscibility gaps even in the liquid phase, no evidence of alloying was observed. Correspondingly, theoretical investigations found that the mixing energy of Ag-Rh clusters did not favor alloying.     

纳米银溶胶中超痕量分子的Raman光谱

根据柠檬酸钠还原硝酸盐的原理制备直径为80~90 nm的银纳米颗粒溶胶, 采用1 mW激光功率和5 s积分时间, 通过表面增强Raman散射技术检测到浓
度为10^-13 mol/L水中的超痕量若丹明6G分子, 通过制备银纳米膜的方法检测到浓度为10^-11 mol/L的超痕量R6G分子. 实验结果表明, 若银纳米颗粒的密度降低, 则其增强Raman散射的能力减弱.     

Ag/TiO2有序多孔复合薄膜的合成及其可见光光催化活性

以自组装SiO2胶体晶体为模板,采用TiCh溶胶凝胶浸渍提拉法制备了TiO2有序多孔薄膜(TIO),然后利用AgNO3液相渗透法将Ag纳米颗粒沉积在TIO上,成功制备了Ag/TiO2有序多孔复合薄膜(ATIO).通过Raman,FESEM,TEM,XPS和Uv-vis等分析手段对复合薄膜进行了表征,结果表明:Ag纳米颗粒的平均尺寸约为10 nm,而且与TiO2晶粒之间有强的相互作用.以亚甲基蓝(MB)水溶液为目标降解物,针对不同Ag/Ti相对原子浓度比的样品,考察了其低功率可见光光催化活性及循环使用性,并与Ag/TiO2无序复合薄膜(ATF)作了对比.研究发现,AgNO3前驱体溶液浓度为10 mmol/L的ATIO样品具有最高的可见光光催化活性,其光降解率是具有相同AgNOa前驱体溶液浓度ATF的3.19倍,显著增强的光催化活性来源于Ag纳米颗粒和TIO有序多孔结构的协同效应.循环降解实验证明样品具有稳定的光催化活性.     

基于金纳米棒可饱和吸收体的Nd:YSAG被动调Q激光器

以新型金纳米材料为可饱和吸收体,研究了LD端面泵浦的Nd:YSAG被动调Q激光器的激光输出特性。实验中通过调整金纳米棒的长径比等参数,成功地将金纳米棒材料由表面等离子体共振引起的非线性吸收峰调控到Nd:YSAG激光的输出波长1 062 nm处,并成功获得了稳定的被动调Q激光输出,在泵浦功率为4.9 W时,激光器的平均输出功率为14 m W,此时,激光脉冲宽度为944.1 ns,重复频率100.1 k Hz。实验结果表明,金纳米材料在脉冲激光领域具有良好的应用前景。     

不同形状的氧化石墨烯-金纳米粒子对对硝基苯酚的表面增强拉曼活性特性分析

通过种子生长法合成了不同形态的金纳米粒子,之后加入至氧化石墨烯水分散液中超声震荡得到不同形状的氧化石墨烯-金纳米粒子复合物。运用扫描电子显微镜、X射线光电子能谱、拉曼光谱等表征手段,探究复合物的表面结构、结合能与电荷状态,通过对对硝基苯酚的检测以表征其拉曼活性,并分析造成不同增强效果的原因。结果表明,氧化石墨烯-金纳米粒子复合物表现出良好的表面增强拉曼活性,可以成功地检测到10^-5 mol/L的对硝基苯酚,且复合物的表面增强拉曼活性因金粒子的形状不同而有所差异。     

纳米银修饰电极的制备及表征

提出一种新颖简单的制备纳米银修饰电极的方法。在金电极表面吸附的氨乙基硫醇(AET)自组装膜固载一价银离子,利用脉冲恒电位法还原制备纳米银修饰电极。从扫描电子显微镜(SEM)可以观察到金电极表面的纳米银颗粒,同时可观察到修饰电极上银的溶出峰。     

基于植酸胶束制备纳米金及其SERS特性研究

在溶液中用替换法合成稳定的拉曼信号较强的金纳米粒子,即首先以植酸为稳定剂和控型剂,用柠檬酸三钠还原硝酸银合成银纳米粒子,再利用银纳米粒子还原氯金酸,在水溶液中制备金纳米粒子.采用紫外-可见(UV-Vis)吸收光谱、透射电子显微镜(TEM)、能量散射光谱(EDX)对金纳米粒子的光学性质及形貌结构进行了表征,实验表明合成的金纳米粒子结构均一、分散性好.以罗丹明6G为探针分子,研究了金纳米粒子作为基底的表面增强拉曼光谱(SERS)效应,结果表明:这种金纳米粒子具有SERS信号强、检测限低、稳定性强等优点.     

表面增强拉曼光谱研究尼古丁与金属纳米粒子的相互作用

以金、银纳米及Au@Ag、Au-Ag合金复合纳米粒子为基底,研究尼古丁分子的表面增强拉曼光谱,讨论分子在4种纳米粒子表面的作用方式及可能的吸附取向.结果表明,分子在金纳米和Au-Ag合金纳米粒子表面的吸附取向相同——垂直吸附,不同的是与金纳米粒子形成了稳定的N-Au键;由于银纳米粒子和Au@Ag核壳纳米粒子表面均富含大...     

Investigation on composite Au /TiO2 nanoparticles (I)

Nanometer sized Au/TiO₂, particles were synthesized by irradiation of a HAuCl₄ solution containing colloidal TiO₂ with light of wavelength (λ) > 330 nm. The absorption maximum attributed to the surface plasmon band of gold was observed at 540 nm, a red shift of about 20 nm from the position in aqueous solution. The Au clusters are situated on the surface of TiO₂ in terms of microcrystallite, which was confirmed by HRTEM, EDS and XRD. The electronic interfaction between the metal and the suport was discussed.     

利用双温模型理论分析飞秒激光烧蚀金过程

为了了解飞秒激光脉冲烧蚀金过程中的电子温度和晶格温度变化。利用显式有限差分法对飞秒激光脉冲烧蚀金的过程中电子和晶格的温度场进行一维数值计算。理论研究了不同激光脉宽和电声耦合系数对金属表层电子和晶格温度的影响,同时还研究了双脉冲激光烧蚀金过程中电子和晶格温度的变化。得出激光脉冲越短,加工热效应越小,多脉冲具有热累积效应。因此,为了实现飞秒激光冷加工,应该采用单个超短脉冲降低热效应。     

Optical nonlinearity and ultrafast dynamics of ion exchanged silver nanoparticles embedded in soda-lime silicate glass

Ag nanoparticles embedded in soda-lime silicate glass were fabricated by ion-exchange and subse-quently annealing method. Z-scan technique, femtosecond time-resolved optical Kerr effect （OKE） technique and femtosecond pump-probe experiment were used to investigate the effects of laser wavelength and laser pulse duration as well as annealing temperature on the third-order optical nonlinearity and ultrafast dynamics of the composites. It was found that the third-order susceptibility of Ag nanoparticles composite glass measured by 400 nm pulse source is larger than that measured by 800 nm pulse source due to an enhancement effect of local field near surface plasmon resonance of Ag nanoparticles in silicate glass. The third-order optical nonlinearity measured by ns laser source is about two orders of magnitude larger than that measured from fs pulse. The annealing temperature has an important effect on the third-order optical nonlinearity and ultrafast dynamics of the composites. Third-order nonlinear susceptibility up to 10^-l0 esu and fast relaxation process up to 0.2 ps have been obtained in Ag nanoparticles doped glass.     

用有效介质理论模拟Ag/AAO纳米有序阵列复合结构光学常数

运用Maxwell—Garnett有效介质理论，计算了Ag／阳极氧化铝（AAO）纳米有序阵列复合结构的光学常数（250～2000nm波段），探讨了Ag组分的体积分数对Ag／AAO光学常数的调制作用和Ag纳米粒子的长径比对其表面等离子共振吸收的影响．模拟结果表明，随着Ag组分体积分数的增加，在小于450nm波段，Ag／AAO复合结构的介电函数实部和折射率均逐渐减小，而介电函数虚部和消光系数逐渐增大；在大于450nm波段，Ag／AAO复合结构的介电函数实部、介电函数虚部及折射率均逐渐增大，消光系数则变化较小．模拟结果显示出Ag纳米粒子的长径比与复合结构表面等离子共振吸收峰位有较强的相关性．另外，理论模拟预期透射谱也与实验透射谱变化趋势一致．     

Synthesis and size control of gold nanoparticles in regular system of amphiphilic molecules

Two synthetic techniques for colloidal gold particles was improved by using SDS. And colloidal Au particles of mean diameters between 5 and 14 nm are synthesized, that exhibit improved monodispersity relative to previously published methods. According to the particular molecular structure of surfactants and different electrons distribution arising from colloidal small sizes and high surface/ volume ratios, it is found that there are a complex between SDS and Au³⁺ (and Au atoms ) during synthesizing colloidal gold nanoparticles and as a stablizer for Au particles, SDS can prevent their further growth. So the colloidal gold particles is monodispersize and more steady. But other surfactants don't affect the process of synthesizing gold nanoparticles because of their structures and properties different from SDS. Gold nanoparticles have considerable bioaffinity and can be applied to study the adsorption of proteins or polypeptides.     

A multiple-labelling method for cells using Au nanoparticles with different shapes

An important and difficult issue is simultaneously identifying the detailed locations of various molecules on the cell surface, as this identification requires a synergistic effect between more than one molecule in a living cell. Au nanoparticles (NPs) with different shapes can be readily recognised under low vacuum scanning electron microscopy (lvSEM). Anisotropic Au nanorods (NRs) possess unique surface plasmon resonance (SPR) properties, which can be further utilised for two photon luminescence (TPL) and other optical imaging techniques. In this paper, Au NRs and Au nanooctahedra (Au NOs) are introduced as biomarkers for ICAM-1 and Integrin β1. Combined with the advantages of lvSEM, this multiple-labelling method is a new method for studying the interactions between specific, functional molecules.     

纳秒激光消融法制备银纳米材料

采用532 nm, 10　ns的激光在丙酮、 水、 甲醇、 异丙醇等溶剂中辐照银金属基 体材料与溶液界面处, 利用超短脉冲激光对金属材料消融, 制备了银纳米粒子溶胶. 通过 紫外/可见/近红外吸收光谱、 透射电子显微镜(TEM)和X射线衍射(XRD)等方法对制备的溶胶 表征, 结果表明, 利用激光消融法可以得到银纳米材料, 溶剂不但影响银纳米粒子的形 成速度, 同时也影响银溶胶的稳定性.     

H2O2增效Ag+掺杂ZnO纳米晶光催化体系降解亚甲基蓝

以水合碳酸锌为前驱体,利用激光复合加热蒸发技术,制得粒径分布均匀,平均粒径在30 nm左右的Ag 掺杂ZnO纳米晶半导体光催化剂.利用UV-Vis,TEM,AFM和XRD等进行了表征.对光催化体系降解亚甲基蓝(MB)的研究表明:悬浮Ag 掺杂ZnO纳米晶的悬浮水相体系中,Ag 的掺杂能有效地改善ZnO对亚甲基蓝的光催化降解性能.此外,H2O2能有效增强Ag 掺杂ZnO纳米晶对MB的降解效率,H2O2浓度为0.05 mol/L时可以使Ag 掺杂ZnO纳米晶的光催化效率提高近1倍.降解产物光谱分析表明:H2O2的存在优先使MB的苯环开环降解,并使其降解更彻底.     

Microstructure and optical absorption properties of Au/NiO thin films

Au nanoparticles dispersed NiO composite films were prepared by a chemical solution method. The phase structure, microstructure, surface chemical state, and optical absorption properties of the films were characterized by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and Uv-vis spectrometer. The results indicate that Au particles with the average diameters of 35–42 nm are approximately spherical and disperse in the NiO matrix. The optical absorption peaks due to the surface plasmon resonance of Au particles shift to the shorter wavelength and intensify with the increase of Au content. The bandwidth narrows when the Au content increases from 8.4wt% to 45.2wt%, but widens by further increasing the Au content from 45.2wt% to 60.5wt%. The band gap E_g increases with the increase of Au contents from 8.4wt% to 45.2wt%, but decreases by further increasing the Au content.     

TiO_2/Ag表面吸附分子的表面增强喇曼散射(SERS)光谱

本文报道了TiO_2/Ag修饰基底材料上吸附分子的表面增强喇曼散射(SERS)光谱研究,通过扫描电镜观察了TiO_2/Ag的表面形貌,研究了Cl~-和激光照射对其SERS光谱的影响.     

Enhancement of Au-Ag-Te contents in tellurium-bearing ore minerals via bioleaching

The purpose of this study was to enhance the content of valuable metals, such as Au, Ag, and Te, in tellurium-bearing minerals via bioleaching. The ore samples composed of invisible Au and Au paragenesis minerals (such as pyrite, chalcopyrite, sphalerite and galena) in combination with tellurium-bearing minerals (hessite, sylvanite and Tellurobismuthite) were studied. Indigenous microbes from mine drainage were isolated and identified as Acidithiobacillus ferrooxidans, which were used in bioleaching after adaption to copper. The effect of the microbial adaption on the bioleaching performance was then compared with the results produced by the non-adaptive process. The microbial adaption enhanced the Au-Ag-Te contents in biological leaching of tellurium-bearing ore minerals. This suggests that bioleaching with adapted microbes can be used both as a pretreatment and in the main recovery processes of valuable metals.