金纳米粒子的电化学合成及光谱表征

采用电化学方法合成各种形状的金纳米粒子,生成的金纳米粒子形貌与施加电流有关,通过匀速递增电流电解的方法,可制备得到哑铃形,球形以及棒状金纳米粒子,采用恒电流电解方法主要获得球形及哑铃形纳米粒子。利用透射电镜、紫外-可见光谱及拉曼光谱对金纳米粒子进行相关表征。紫外-可见光谱研究发现金纳米棒出现位于近红外区间的吸收峰(985 nm),由此推测棒的长径比约为6。以结晶紫为探针分子,研究了金纳米粒子的表面增强拉曼光谱(SERS)效应,并分析得出其平躺的吸附模式。根据形貌表征的结果推断了纳米粒子的生长机理。     

金纳米棒状微粒的胶囊模型及吸收光谱

提出了金纳米棒状微粒的胶囊模型,用Waterman发展的T矩阵方法计算了金纳米棒状微粒的吸收光谱.计算谱和实验谱基本符合,520 nm左右处的吸收峰对应于金纳米棒的横向表面等离体子共振（横模）,长波长处的吸收峰对应于金纳米棒的纵向表面等离体子共振（纵模）.随着金纳米棒纵横比的增加,纵模吸收峰表现出显著的红移,横模吸收峰则微弱地蓝移.此外,计算结果表明,金纳米棒状微粒外部介质的介电常数必须随着金纳米棒纵横比的增大非线性地减小.     

球型和棒状金纳米粒子的光谱性质比较

柠檬酸钠还原和诱导晶种生长法合成了球型和棒状金纳米粒子。金纳米粒子的吸收光谱表明,表面等离子体共振(SPR)强烈依赖于金属粒子的形状,球型粒子表现为单-SPR谱峰,而棒状粒子则具有横向和纵向SPR谱峰,且纵向SPR峰位和强度取决于棒状粒子的径横比。棒状金纳米粒子对吸附的对巯基苯甲酸分子的拉曼散射比球型金纳米粒子具有更强的表面增强性能,归因于棒状粒子高能晶面上的吸附可能导致的更强的化学增强效应。     

金纳米棒复合体的消光特性

金属纳米颗粒局域表面等离激元共振时能够产生消光和近场增强效应已经成为国内外研究的热点. 应用时域有限差分法对L形纳米棒与普通纳米棒构成的金纳米棒复合体的消光光谱及其近场增强和电流矢量密度分布进行了研究. 计算结果表明, 普通纳米棒和L形纳米棒二聚体的光谱响应与纳米棒间的间距有关, 而金纳米棒复合体的消光光谱可通过调整L形纳米棒与普通纳米棒间的间距、L形纳米棒的臂长度以及普通纳米棒的长度进行调谐. 此外金纳米棒复合体可以分解成L形纳米棒二聚体和普通纳米棒二聚体两个部分, 通过分别改变L形纳米棒的臂长和普通纳米棒的长度, 对比L形纳米棒二聚体和普通纳米棒二聚体间的共振峰位置变化, 可以更直观地了解金纳米棒复合体消光光谱线型的变化. 这些结果可用于指导金纳米棒复合体纳米光子器件的设计, 以满足其在表面增强拉曼散射和生物传感等方面应用.     

热蒸发法制备的球棒状氧化锌晶体的形貌及生长过程

在不用催化剂的条件下,通过热蒸发锌粉的方法,一种新颖的球棒状的氧化锌纳米结构被沉积在硅基片上.每一根球棒状的氧化锌纳米棒("纳米球棒")由三部分构成,分别是六边形"球棒头"、"球棒把手"以及一个连接过渡的部分.高分辨率透射电镜和选区电子衍射结果表明,纳米棒呈单晶特性,沿着[0001]方向择优生长.根据对实验结果的分析,纳米球棒的生长过程可以利用气-固生长机制进行解释,合理地提出其生长模型.     

一种新型银溶胶的制备、表征及其SERS活性的研究

报道了用一种化学还原方法制备银溶胶的新方法。用紫外-可见光谱和透射电镜研究银纳米粒子的形成过程,粒子形状及粒径分布。结果表明,在反应初期形成球形和棒状两种形状的银纳米粒子,随着反应的进行,大部分的棒状粒子逐渐变为球形粒子,最终棒状粒子少于银纳米粒子总数的3%。因此,最终得到了一种形状均一的,平均粒径为17nm银纳米粒子。同时也用紫外-可见光谱研究了Cl-的加入对这种银纳米粒子光谱性质的影响,结果表明Cl-加速了银纳米粒子的聚集。这种银溶胶有着较高的SERS活性。     

金纳米棒核／二氧化硅壳纳米复合结构的可控制备及细胞成像

采用模板合成以及溶胶凝胶方法制备了金纳米棒核／二氧化硅壳（GNR@SiO2）纳米复合粒子,探讨了这种新型纳米复合结构的可控制备、光谱性质、细胞毒性和细胞成像。通过紫外可见分光光度计、透射电镜、共聚焦显微镜对样品进行表征,结果表明：通过对反应时间的调控,获得的纳米复合粒子的二氧化硅壳层厚度可以控制在20～30nm。由于二氧化硅壳层的存在,大大提高了金纳米棒的稳定性,同时降低了金纳米棒的细胞毒性;此外,由于二氧化硅壳层具有良好的化学修饰作用,因此可以将荧光探针分子标记在二氧化硅壳层表面,修饰后的纳米复合粒子可以通过细胞内吞作用进入细胞,从而实现细胞内的光学成像。因此,该纳米粒子复合材料在生物传感、细胞成像以及光热治疗等方面有着良好的应用前景。     

半胱氨酸修饰金纳米棒光学性质的研究

采用种子生长法制备了不同长径比的金纳米棒,并通过金硫键的结合在其表面包覆半胱氨酸分子。利用紫外-可见吸收光谱仪,扫描电子显微镜以及拉曼光谱仪等对样品进行分析和表征。实验结果表明金纳米棒产率较高,且一致性较好。表面修饰后的金纳米棒的纵向吸收峰发生蓝移,表明半胱氨酸分子与金纳米棒的结合有助于溶液分散性的提升。以结晶紫为探针分子,随着金纳米棒长径比的增加其拉曼增强效果变强。进一步分析发现,修饰后的金纳米棒的表面增强拉曼光谱的增强效果并未受到影响。通过金纳米棒与半胱氨酸分子牢固的结合,一方面可以提高金纳米棒溶液的分散性与稳定性;另一方面半胱氨酸分子可为金纳米棒修饰其它有机官能团提供了一个牢固的桥梁,有效地拓展了金纳米棒的应用方向。     

介孔SiO2纳米棒的制备及其表面锚接金纳米粒子

 以正硅酸乙酯为硅源,十六烷基三甲基溴化铵为模板剂,聚乙二醇为分散剂,采用溶胶-凝胶法制备出SiO₂纳米粒子,应用透射电镜、扫描电镜、X射线衍射仪、红外光谱仪和X射线能谱仪研究了粒子的性能。结果表明：所得产物是具有周期性规则介孔的棒状粒子,长径比随着硅源、模板剂和分散剂浓度的降低而减小;向反应体系中引入乙醇,随着乙醇与水的体积比例的增加,粒子由棒状向球状转变,进而形成不规则絮状凝聚体。用硅烷化技术对SiO₂纳米棒表面进行修饰后吸附平均粒径3.7 nm的金种子,再用多轮生长法使种子长大,经过30轮生长,种子平均粒径增大至59 nm,得到了SiO₂-Au复合纳米体系。透射电镜和紫外-可见分光光度计分析结果表明：金纳米粒子锚接在SiO₂纳米棒表面的某些点位,呈分散分布;复合体系表现出强烈的金的表面等离子体共振吸收峰,该峰随着金粒子的粒径增大,在500~700 nm波段内红移。     

聚苯胺纳米颗粒及纳米棒的分子链结构研究

通过调节浓硫酸和苯胺单体的摩尔比,采用电化学沉积法制备了聚苯胺(Polyaniline,PANI)纳米粒子和纳米棒。利用拉曼光谱技术研究了PANI纳米颗粒和纳米棒分子链的结构特征,结果表明PANI纳米颗粒的分子链结构主要是苯式结构,而PANI纳米棒的分子链主要是醌式结构。另外,随着电化学沉积时间的增加,尽管PANI在生长过程中表现出不同的结构特性,但是电化学沉积15min后,两种结构的PANI基本生长完善。     

Adsorptions and diffusions of carbon atoms on the surface and in the subsurface of Co （200）： A first-principles density-functional study

First-principles calculations based on density functional theory are used to investigate the adsorptions and diffusions of carbon atoms on the surface and in the subsurface of Co(200). The preferred site for the carbon atom on the surface is the hollow site, and the preferred site in the subsurface is the octahedral site. There is charge transfer from the surface to the adsorbed carbon atom, and for the most favorable adsorbed structure the charge transfer is largest. Moreover, the energy barriers for the diffusions of carbon atoms on the surface and from the surface into the subsurface and then back to the surface are calculated in detail. The results indicate that the energy barrier for the diffusion of carbon atoms on the surface is comparable to that from the subsurface to the surface. The results imply that both the direct surface nucleation and the surface segregation from Co bulk can be observed in the chemical vapor deposition growth of graphene on Co(200)substrate, which can gain a new insight into the growth mechanism of graphene.     

双核Au配合物激发态性质的理论研究

用二阶微扰方法和单组态相互作用方法分别计算了双核Au配合物Au2(SNHCH)2(a),Au2(SN2C4H3)2(b)和Au2(SN2C2H-C6H4)2(c)基态的几何结构,并在此基础上用含时密度泛函方法计算了它们的光谱。a,b,c所具有的芳香结构是逐渐增加的。计算结果表明:芳香结构的增加会加强Au之间的相互作用;在磷光发光过程中,各金属配合物都具有C(p)/芳香环(p)→S(p)跃迁属性(LLCT)、Au(p)→Au(d)电荷转移(MCCT)属性、C(p)/芳香环(p)→Au(d)跃迁属性(LMCT)和芳香环内部p电子跃迁属性(LLCT),但随着a、b、c所具有的芳香结构的增加,Au(p)→Au(d)的电荷转移(MCCT)逐渐减弱,C(p)/芳香环(p)→Au(d)的跃迁(LMCT)也逐渐减弱,芳香环内部p电子跃迁(LLCT)属性逐渐增强,即芳香结构会改变双核Au配合物的发光性质。     

Electron‐transfer transparency of graphene: Fast reduction of metal ions on graphene‐covered donor surfaces

The mechanism of charge transfer through nanomaterials such as graphene remains unclear, and the amount of charge that can be transferred from/to graphene without damaging its structural integrity is unknown. In this communication, we show that metallic nanoparticles can be decorated onto graphene surfaces as a result of charge transfer from the supporting substrate to an adjoining solution containing metal ions. Au or Pt nanoparticles were formed with relatively high yield on graphene‐coated substrates that can reduce these metal ions, such as Ge, Si, GaAs, Al, and Cu. However, metal ions were not reduced on graphene surfaces coated onto non‐reducing substrates such as SiO₂ or ZnO. These results confirm that graphene can be doped by exploiting charge transfer from the underlying substrate; thus graphene is not only transparent with respect to visible light, but also with respect to the charge transfer. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Effect of aspect ratio on the inter-surface plasmonic coupling of tubular gold nanoparticle

A theoretical study based on discrete dipole approximation (DDA) and coupling effect is presented on the tunable transverse surface plasmon resonance (SPR) in a gold nanotube with varying aspect ratio (AR). Because gold nanotube has the shape features from both rod and shell, both the AR and wall thickness can greatly affect the transverse SPR. It is observed that the maximum red shift can be obtained with small wall thickness and AR. By calculating the local field distribution, the physical mechanism of this multi shape factors controlled plasmon shifting has been illustrated by the coulombic interaction from the charges at the interfaces of gold nanotube. This study indicates that finding the surface charge distribution by calculating the local electric field can be used as an effective method to analyze the plasmonic characters in complicated metallic nanostructure.     

Photo-induced charge transfer emission in (E)-3-(4-dimethylamino-naphthalen-1-yl)-acrylic acid and its use as metal ions fluorosensor

In this study, spectroscopic properties of (E)-3-(4-dimethylamino-naphthalen-1-yl)-acrylic acid (DMANAA) have been explored using absorption and emission spectroscopy in combination with quantum chemical calculations. In addition to the local emission, the molecule shows a red-shifted emission from the charge transfer state. The charge transfer emission band is found to be dependent on polarity and hydrogen-bonding ability of the solvents. This photo-induced charge transfer process has been explored theoretically at Density Functional Theory level using twisted intramolecular charge transfer model. Structural calculations and potential energy surfaces along the donor twist coordinate done by Density Functional Theory correlate well with the spectroscopic observations. Addition of metal ions to DMANAA solutions in acetonitrile solvent shows progressive quenching of the charge transfer band and growth of a blue-shifted band, making way for its use as a good fluorosensor for various metal ions.     

Comment on “electron energy-loss spectra of CO-adsorbed Ni(100) surfaces” by K. Akimoto et al

The experimental ELS results obtained by Akimoto et al. [1] are confronted with the corresponding UPS peaks taking into account both charge transfer and plasmon screening relaxation processes. The charge transfer mechanism leads to consider ionization as well as inter-orbital (direct) transitions in the ELS spectra. Within this scheme, new assignments are proposed for the experimental energy-loss lines.     

空气-水蒸气流经扰流圈的冷凝传热强化

本文对含高浓度不凝组分存在条件下水蒸汽冷凝传热强化进行了机理分析和实验．结果表明,扰流圈能大大增加气液边界层的湍动强度,具有优越的强化传热、传质效果．在实验范围内,其冷凝传热膜系数是光滑管的１．９～３．５倍．     

Controlling growth of ZnO rods by polyvinylpyrrolidone (PVP) and their optical properties

ZnO rods with different morphologies were synthesized through a wet chemical method by addition of polyvinylpyrrolidone (PVP). By adjusting the concentration of the additive in the growth solution, we can control the diameter, ratio of length to diameter and density of ZnO rods. FESEM images showed that the rods in nanoscale could be obtained at the polyvinylpyrrolidone concentration of 1.0 mM. Meanwhile, the resonant Raman scattering and photoluminescence spectra showed that the crystalline quality and the optical property of ZnO rods were improved through moderate addition of polyvinylpyrrolidone (concentration of 1.0 mM) in the growth solution. In addition, the possible mechanism of the PVP effect on the growth of ZnO rods was discussed based on the FT-IR spectra.     

晶体C_3H_7NO_2:VO~(2+)的自旋哈密顿参数及局域结构

在晶体场理论(CF机制)和电荷转移机制(CT机制)的基础上,结合双自旋-轨道耦合参量模型、自旋哈密顿量的高阶微扰公式及晶场能量公式计算得到C_3H_7NO_2:VO~(2+)晶体的自旋哈密顿量(EPR参量)和吸收光谱,及电荷转移跃迁能级.对比只采用CF机制和采用双重机制下的计算结果,发现高价钒离子(V~(4+))掺杂在C_3H_7NO_2晶体中的CT机制对于其EPR参量的影响不能忽略.     

P-thiocresol 吸附在银纳米粒子表面系统的表面增强拉曼散射和表面增强共振拉曼散射的增强研究

文中从实验和计算两方面报道了在514.5 nm激发光下P-Thiocresol吸附在银胶表面系统的表面增强拉曼散射(SERS).文中分析了它的增强机制,发现增强主要来自于电磁场增强.如果考虑距离为2nm的两个银纳米粒子的耦舍效应,两粒子之间的SERS的电磁场增强为7.16 × 107.静态化学增强亦起到部分增强作用,它的增强倍数为6.所以,总的SERS增强,包括静态化学增强和电磁场增强,是Gtotal=Gsc ×GEM=4.4×108.我们也理论地研究了此系统的表面增强共振拉曼散射(SERRS).当激发光与P-Thiocresol-Ag3系统的激发态共振时,电荷转移机制(化学增强)也将起到重要作用,最强的增强可迭106.我们使用电荷密度将激发光下p-Thlocresol和Ag团簇问的电荷转移结果可视化,这是电荷转移的直接理论证据.对于SERRS增强,包括电荷转移和电磁场增强机制,能达到1013.