树枝状纳米银颗粒的制备与电活性

在Ag(NH3)2+溶液中,在钛基体上电沉积出树枝状纳米银颗粒,研究了沉积电位对树枝状纳米银颗粒形成的影响,探讨了这种树枝状纳米银颗粒形成的机理,并研究了这种钛基树枝状纳米银电极(Ag/Ti)在碱性溶液中对甲醛氧化的电催化活性。结果表明,在30 mmol/LAg(NH3)2+以及沉积电位在-1.8～-1.2 V(vsAg)时,形成了形态为树枝状的纳米银颗粒。在沉积电位为-1.6 V(vs Ag),Ag(NH3)2+浓度为30 mmol/L的溶液中,电沉积制备的这种树枝状纳米银电极(Ag/Ti)对甲醛氧化具有强的电催化活性。循环伏安曲线表明,在0.1 mol/LNaOH溶液中以及甲醛的浓度范围在0～40 mmol/L,甲醛浓度和它的氧化峰电流密度呈现良好的线性关系,检测下限达到0.662 mmol/L,这种新型的树枝状纳米银电极有望作为甲醛检测的传感器。     

金银纳米粒子的复合组装及表面增强拉曼光谱研究

采用自组装技术在硅基底上进行金银纳米粒子的混合组装, 通过控制组装溶液中金银溶胶的体积比而控制基底上金银纳米粒子的密度. SEM结果显示金银呈亚单层均匀分布, 以吡啶为探针分子, 在不同波长的激发光下研究了纯金、银以及混合组装时的SERS效应. 利用金银在不同激发线下增强效应的不同以及探针分子吸附在金银纳米粒子表面主要谱峰相对强度差别的特点, 通过一系列校正以及差谱方法研究了金银共存时SERS效应的变化, 并分离出混合体系中金的增强行为, 结果表明在金银同时组装时吡啶的SERS谱峰特征主要表现为银纳米粒子的行为, 分离出的金SERS光谱特征接近银的行为, 说明金银纳米粒子之间产生了一定的耦合作用.     

Fabrication of Ag/Au bimetallic nanoparticles by UPD-redox replacement: Application in the electrochemical reduction of benzyl chloride

The bimetallic Ag/Au nanoparticles were prepared by underpotential deposition-redox replacement technique on the basis of Au nanoparticles modified glassy carbon (GC) electrode. The as-prepared Ag/Au nanoparticles were characterized by scanning electron microscopy and energy-dispersive X-ray spectroscopy. The Ag/Au bimetallic nanoparticles modified GC electrode with low-Ag loading exhibits much better catalytic activity for the reduction of benzyl chloride than Ag nanoparticles modified GC electrode. The result is attributed to the synergic effect between Ag and Au in the reduction process. The chronoamperometry test shows that the Ag/Au nanoparticles possess long-term performance in the electrolysis.     

Spontaneous formation of core/shell bimetallic nanoparticles: a calorimetric study

We showed recently that low entropy core/shell structured nanoparticles form spontaneously from the physical mixture of a dispersion of Ag nanoparticles and that of another noble metal (Rh, Pd, or Pt) at room temperature. Here we use isothermal titration calorimetry (ITC) and show that the initial step of such a spontaneous process is strongly exothermic. When the alcohol dispersion of poly(N-vinyl-2-pyrrolidone) (PVP)-protected Rh nanoparticles (average diameter 2.3 nm) was titrated into the alcoholic dispersion of PVP-protected Ag nanoparticles, a strong exothermic enthalpy change, DeltaH, was observed: DeltaH = -908 kJ/mol for Ag(S) nanoparticle (average diameter 10.8 nm) and -963 kJ/mol for Ag(L) nanoparticles (average diameter 22.5 nm). The strength of interaction increases in the order of Rh/Ag > Pd/Ag > Pt/Ag. This strong exothermic interaction is considered as a driving force to from low entropy bimetallic nanoparticles by simple mixing of two kinds of monometallic nanoparticles. We show also that exothermic interactions occur between a pair of noble metal nanoparticles themselves by using ITC.     

Ag_核Au_壳金属复合纳米粒子的制备及表面增强拉曼光谱研究

在已制备好的Ag纳米粒子表面,通过化学还原的方法沉积生长Au包裹层,制备了粒子尺寸为50-70nm的Ag核Au壳复合纳米粒子.通过改变AuCl₄^-量,使Ag_100-xAu_x中Au的含量由x=0变为x=30.用UV-Vis吸收光谱和透射电子显微镜(TEM)对该结构纳米粒子进行了表征,并以对巯基苯胺(PATP)为探针分子进行表面增强拉曼光谱(SERS)研究.表面拉曼光谱表明,该结构的纳米粒子具有比Ag更强的SERS活性,随着Au:Ag比例的逐渐增加,其活性呈现先增大后减小的趋势,其最大增强约为Ag纳米粒子的10倍.     

Silver Nanoparticles by PAMAM-Assisted Photochemical Reduction of Ag(+)

The photochemical synthesis of Ag(0) nanoparticles in the presence of amino- and carboxylate-terminated PAMAM dendrimers is reported. The formation of Ag(0) nanoparticles was followed spectrophotometrically and by transmission electron microscopy (TEM). According to TEM investigations Ag(0) nanoparticles with the average size of about 7 nm in diameter were produced. Based on the present investigation a possible mechanism for the Ag(0) nanoparticles formation is proposed. Copyright 2000 Academic Press.     

Ag/DNQ-novolac-based nanocomposite films for controllable UV lithography morphological patterning

In this study, the detailed characterisation of silver (Ag) nanoparticles/polymer nanocomposite chemical structure and morphology of grating has been carried out. Scanning electron microscopy measurements show spherical shape of Ag nanoparticles (40–80 nm in diameter) prepared in chloroform by reduction of silver nitrate. In the positive photoresist based on 2-diazo-2H-naphthalen-1-one (DNQ)–novolac, Ag nanoparticles were deposited from organic colloidal solution. The content of nanoparticles in the polymer matrix was varied by increasing the concentration of Ag colloidal solution. Grating was formed by contact lithography. The quantification of Ag nanoparticles and chemical analysis of Ag/DNQ-novolac-based nanocomposite was performed by means of energy dispersive X-ray analyzer and SEM/EDS. In order to study the effect of Ag nanoparticles on the DNQ-novolac-based nanocomposite structure, investigations with Fourier transform infrared spectroscopy were conducted. Ag nanoparticles cause changes associated with substituent-sensitive out-of-plane C–H bending vibrations of aromatic ring. Ag/DNQ-novolac-based nanocomposite film surface morphology and grating topography imaging were performed using atomic force microscopy. Added Ag nanoparticles change the geometrical parameters of the gratings. The split of corrugations was achieved in Ag/DNQ-novolac-patterned films. Their morphology can be tailored by altering the content of Ag nanoparticles.     

光催化合成金属Ag纳米颗粒的生长机制——晶核密度控制的生长模式转换

利用AgNO3水溶液,通过严格控制TiO2薄膜的化学活性,系统研究了在TiO2表面光催化合成金属Ag纳米颗粒的生长行为。研究发现,光催化合成金属Ag纳米颗粒存在着两个完全不同的生长机制,分别对应着金属Ag纳米颗粒的各向同性和各向异性生长。当溶液浓度较低时,Ostwald熟化(OR)机制主导着金属Ag纳米颗粒的长大过程;当溶液浓度较高时,取向附生(OA)机制决定着金属Ag纳米颗粒长大成纳米片。原位消光光谱分析表明,OR机制和OA机制生长的前期具有相近消光特征,决定金属Ag纳米颗粒生长模式的关键是AgNO3溶液的浓度,更准确地说是金属Ag初级晶核的局域密度。在此基础上提出了有关光催化合成金属Ag纳米颗粒的生长模型。     

核壳纳米粒子与牛血清白蛋白表面增强拉曼光谱的研究

本文用表面增强拉曼光谱(SERS)系统地研究了牛血清白蛋白(BSA)与Ag/Pt核壳纳米粒子的相互作用,特别是核壳纳米粒子与被吸附的牛血清白蛋白分子之间的界面作用,并用紫外可见光谱、圆二色光谱(CD)作为辅助手段进一步证实了BSA与核壳纳米粒子的作用状况.通过紫外光谱研究发现,核壳纳米粒子的特征吸收峰的消失表明纳米粒子完全被牛血清白蛋白包覆.用近紫外CD光谱探讨了血清白蛋白的芳基氨基酸(苯丙氨酸、酪氨酸)残基微环境的变化.为探讨牛血清白蛋白与Ag/Pt核壳纳米粒子的作用机理及纳米尺寸的生物效应奠定了理论基础.     

光催化合成金属Ag纳米颗粒的生长机制——晶核密度控制的生长模式转换

利用AgNO₃水溶液,通过严格控制TiO₂薄膜的化学活性,系统研究了在TiO₂表面光催化合成金属Ag纳米颗粒的生长行为。研究发现,光催化合成金属Ag纳米颗粒存在着两个完全不同的生长机制,分别对应着金属Ag纳米颗粒的各向同性和各向异性生长。当溶液浓度较低时,Ostwald熟化（OR）机制主导着金属Ag纳米颗粒的长大过程;当溶液浓度较高时,取向附生（OA）机制决定着金属Ag纳米颗粒长大成纳米片。原位消光光谱分析表明,OR机制和OA机制生长的前期具有相近消光特征,决定金属Ag纳米颗粒生长模式的关键是AgNO₃溶液的浓度,更准确地说是金属Ag初级晶核的局域密度。在此基础上提出了有关光催化合成金属Ag纳米颗粒的生长模型。     

SERS-activating effect of chlorides on borate-stabilized silver nanoparticles: formation of new reduced adsorption sites and induced nanoparticle fusion

Changes in morphology, surface reactivity and surface-enhancement of Raman scattering induced by modification of borate-stabilized Ag nanoparticles by adsorbed chlorides have been explored using TEM, EDX analysis and SERS spectra of probing adsorbate 2,2'-bipyridine (bpy) excited at 514.5 nm and evaluated by factor analysis. At fractional coverages of the parent Ag nanoparticles by adsorbed chlorides <0.6, the Ag colloid/Cl(-)/bpy systems were found to be constituted by fractal aggregates of Ag nanoparticles fairly uniform in size (10 +/- 2 nm) and SERS spectra of Ag(+)-bpy surface species were detected. The latter result was interpreted in terms of the presence of oxidized Ag(+) and/or Ag(n)(+) adsorption sites, which have been encountered also in systems with the chemically untreated Ag nanoparticles. At chloride coverages >0.6, a fusion of fractal aggregates into the compact aggregates of touching and/or interpenetrating Ag nanoparticles has been observed and found to be accompanied by the formation of another surface species, Ag-bpy, as well as by the increase of the overall SERS enhancement of bpy by factor of 40. The same Ag-bpy surface species has been detected under the strongly reducing conditions of reduction of silver nitrate by sodium borohydride in the presence of bpy. The formation of Ag-bpy is thus interpreted in terms of the stabilization of reduced Ag(0) adsorption sites by adsorbed bpy. The formation of reduced adsorption sites on Ag nanoparticle surfaces at chloride coverages >0.6 is discussed in terms of local changes in the work function of Ag. Finally, the SERS spectral detection of Ag-bpy species is proposed as a tool for probing the presence of reduced Ag(0) adsorption sites in systems with chemically modified Ag nanoparticles.     

银纳米粒子的绿色合成及其对荧光素室温磷光的增强效应

以β-环糊精(β-CD)作为稳定剂, 葡萄糖为还原剂, 银氨溶液为前驱体, 实现了绿色化学方法合成银纳米粒子. 利用紫外-可见分光光度法(UV-Vis)、高分辨透射电镜(HRTEM)、红外光谱法(FTIR)对产物进行了表征. 将银纳米粒子引入滤纸表面增强室温磷光(RTP)的研究, 发现银纳米粒子对醋酸铅诱导荧光素(FL)所得的RTP具有明显的增强效应, 并且随着银纳米粒子加入量的增加具有先增强后猝灭的趋势. 对β-CD与银纳米粒子的相互作用机理及银纳米粒子对FL RTP增强效应的作用机理进行了初步讨论.     

纳米TiO2对Ag(I)配合物的吸附

利用纳米TiO2的表面吸附活性, 以[S2O3]2-为络合剂, 应用火焰原子吸收光谱检测方法, 高效吸附分离了水中痕量Ag(Ⅰ). 系统研究了纳米TiO2的晶体结构、溶液的pH值、吸附时间、Ag(Ⅰ)的起始浓度及常见共存离子对吸附率的影响, 确定了最佳吸附条件. FTIR光谱分析结果表明, Ag(Ⅰ)配合物以物理作用吸附在纳米TiO2颗粒表面. 纳米TiO2对Ag(Ⅰ)的吸附等温线为S型, 表现出多分子层吸附特征. 硝酸和硫脲混合溶液可将吸附在TiO2纳米颗粒表面的Ag(Ⅰ)全部洗脱.     

Ag/Au纳米粒子的没食子酸还原制备及其共振瑞利散射光谱测定人血清总蛋白

以没食子酸为还原剂和稳定剂,用种子生长法制备出粒径均匀、单分散性和稳定性好、近球形的Ag/Au 核壳纳米粒子.高分辨透射电镜(HRTEM)与 X-射线能量色散光谱仪(EDX)测试表明,在Ag/Au摩尔比为1:1.6时,Au已完全包裹在Ag纳米粒子表面时,平均粒径为25 nm.以此摩尔比制备的Ag/Au核壳纳米粒子为探针...     

光诱导转化法制备单晶Ag纳米三棱体和立方体

The preparation of Ag nanoparticles with the non-spherical shape has been conducted from aqueous solution by photo induced conversion. Ag nanoprisms (80～120nm) and nanocube s(90～200nm) were respectively obtained in the presence of trisodiumcitrate (TSC) orpolyvinylpirrolidon (PVP). These Ag nanoparticles were single-crystals. The results showed that Ag nanoprisms had apreferential growth direction along the Ag(111) axis and Ag nanocubes had a preferential growth direction along the Ag(100) axis. By means of characterization with TEM, ED and UV-V is Spectra, the fundamental analyses and discussion about the changing causes of nanoparticles shape from spherical tonon-spherical have been carried out in the photo induced process.     

Ag, Ag2S, and Ag2Se nanocrystals: synthesis, assembly, and construction of mesoporous structures

Synthesis of mesoporous materials has become more and more important due to their wide application. Nowadays, there are two main ideas in their preparation. One is focused on the templating method. The other is based on metal-organic frameworks (MOFs) constructed from molecular building blocks. Herein, we exploit a new idea for their facile and general synthesis, namely, using "artificial atoms" (monodisperse nanoparticles) as uniform building blocks to construct ordered mesoporous materials. Mesoporous Ag, Ag2S, and Ag2Se have been obtained to demonstrate this concept. On the other hand, we also describe a facile method to prepare the "building blocks". Ag nanoparticles were obtained by direct thermal decomposition of AgNO3 in octadecylamine, and Ag2S/Ag2Se nanoparticles were synthesized by reaction between sulfur or selenium powder and Ag nanoparticles formed in situ. This approach for Ag, Ag2S, and Ag2Se nanoparticles is efficient, economical, and easy to scale up in industrial production.     

表面修饰Ag_2S纳米微粒的合成及摩擦学行为研究

在水醇混合介质中,采用同阳离子共沉淀法合成了有机化合物表面修饰的Ａｇ２Ｓ纳米微粒,在高速钢基底上制备成膜,研究了它的摩擦学特性。结果表明：修饰后的Ａｇ２Ｓ纳米微粒粒径小,性能稳定,在有机介质中分散成透明溶液。ＡｇＤＤＰ膜和Ａｇ２Ｓ ＤＤＰ膜均可显著降低钢基底的摩擦系数。研究证实表面修饰Ａｇ２Ｓ纳米微粒的摩擦作用机制是在较低负荷下表面修饰层起主要作用,在较高负荷下Ａｇ２Ｓ纳米核起主要的承载和减摩抗磨作用。     

Spontaneous formation of Ag nanoparticles in dimethylacetamide solution of poly(ethylene glycol)

The spontaneous formation of Ag nanoparticles in a dimethylacetamide (DMAC) solution of poly(ethylene glycol) (PEG) was studied. FTIR analysis showed the formation of carbonyl groups, revealing that PEG acted as not only a protective agent but also a reducing agent in the formation of Ag nanoparticles. Since no significant reactions were observed when poly(tetramethylene glycol) (PTMG) was used to replace PEG or acetonitrile was used to replace DMAC, it was suggested that PEG molecules might be coiled to form pseudo-crown ether cavities, in which Ag complexes were bound to the oxyethylene groups and reduced, and that the use of a solvent which might appropriately solvate the Ag salt was important for the formation of Ag nanoparticles. In addition, the mean diameters of the resultant Ag nanoparticles were 3.8-9.0 nm, increasing with increasing AgNO(3) concentration. A sufficiently high PEG concentration relative to AgNO(3) was necessary for the formation of smaller Ag nanoparticles. This work provided a simple route for the in situ synthesis of Ag nanoparticles.     

Laser-assisted synthesis of Au-Ag alloy nanoparticles in solution

By using laser-induced heating, we prepared Au-Ag nanoalloys via three different procedures: (i) mixture of Au nanoparticles and Ag(+) ions irradiated by a 532 nm laser, (ii) mixture of Au and Ag nanoparticles irradiated by a 532 nm laser, and (iii) mixture of Au and Ag nanoparticles irradiated by a 355 nm laser. Procedure i is advantageous for the production of spherical alloy nanoparticles; in procedures ii and iii, nanoalloys with a sintered structure have been obtained. The morphology of the obtained nanoalloys depends not only on the laser wavelength but also on the concentration of nanoparticles in the initial mixture. When the total concentration of Ag and Au nanoparticles in the mixture is increased, large-scale interlinked networks have been observed upon laser irradiation. It is expected that this selective heating strategy can be extended to prepare other bi- or multi-metallic nanoalloys.     

纳米银对表面吸附镝配合物的荧光增强效应研究

研究了不同粒径的纳米银对镝配合物(乙二胺四乙酸配合物)的光谱学性质影响。当配合物溶液的pH值范围为4.0～6.0时,加入纳米银,可观察到大量的纳米银聚集体形成,而在吸收光谱的长波处出现一个新的吸收峰,随着纳米银浓度的增加,该吸收峰逐渐红移,同时,镝配合物的荧光强度增强。实验结果表明,纳米银粒子对镝配合物的荧光增强效应及荧光增强因子与纳米银粒子的浓度和粒径密切相关。随着纳米银浓度的增加,配合物的荧光强度先增强而后又逐渐降低。小粒径的纳米银对镝配合物的荧光增强因子较小。本文从纳米银粒子的聚集效应、局部电磁场增强效应及光吸收效应等方面探讨了纳米银对表面吸附镝配合物的+荧光增强效应机理。