Au/Ag芯-壳复合结构纳米颗粒的制备和表征

利用二步液相还原法制备了 Au/Ag 芯 壳复合结构的纳米颗粒。用 TEM对反应液中金离子和银离子的摩尔比分别为1∶2和1∶1时所制备的 Au/Ag芯 壳复合结构的纳米颗粒的尺寸和形貌进行了表征。其紫外 可见吸收光谱具有 2 个可区分的吸收带,与纯金和纯银纳米颗粒的光学吸收特性对比后认为:随着反应液中银离子摩尔份数的增加,等离子体共振吸收峰始终位于 410nm附近的吸收带为银纳米颗粒的等离子体吸收带;另一个将随之产生蓝移的吸收带为Au/Ag芯 壳复合结构纳米颗粒的等离子体吸收带,蓝移是由于银壳厚度的增加而引起的。     

自组装Ag纳米颗粒的表面等离子体共振及其对CdSe量子点的荧光增强效应

采用柠檬酸三钠还原硝酸银的方法制备了Ag纳米粒子溶胶,利用静电自组装技术制得单分散Ag纳米颗粒薄膜.研究了该Ag纳米颗粒薄膜的光学特性,通过改变反应物浓度和后期的热退火温度,有效调控了Ag纳米颗粒尺度和其在外场作用下产生的表面等离子体共振(SPR)特性.将所制备的Ag纳米颗粒薄膜与CdSe量子点耦合,利用SPR对荧光的...     

Ag/Cu离子先后注入形成合金和核壳结构纳米颗粒

具有核壳结构的纳米颗粒由于它独特的性质已经成为目前材料科学研究的热点.本文介绍用离子注入并退火的方法制备核壳结构的纳米颗粒.Ag/Cu离子以13的剂量比先后注入到非晶SiO2中形成了Ag-Cu合金纳米颗粒.当样品在还原气氛中600℃退火后,光学吸收谱在400nm附近出现了一个新峰,透射电子显微镜(TEM)观察发现纳米颗粒中心出现亮的衬度,相应的选区电子衍射(SAED)出现了两套斑点,因而形成了Ag-Cu合金核Cu壳纳米颗粒.用Mie理论模拟了核壳结构光学吸收谱,其结果与实验符合较好.     

硝酸银含量对Au@Ag_2S@ZnS双壳核壳结构的形成及其光学性能影响的研究

采用化学还原法先制备了表面吸附有十六烷基三甲基溴化铵的金纳米颗粒,然后以金纳米颗粒为籽晶,采用二乙基二硫代氨基甲酸锌和硝酸银分别作为锌源和银源,通过水热反应法制备出了Au@Ag2S@Zn S双壳核壳结构。XRD分析表明样品中含有立方相的Au、单斜相的Ag2S与六方相的Zn S。UV-Vis谱揭示样品的等离子体共振峰位可以通过改变硝酸银的加入量而控制。SEM和TEM图像显示样品呈球形且壳层由许多小的纳米颗粒聚集而成,Zn S壳层为多晶。由光致发光谱分析得知,随着硝酸银量的增加,主发光峰先是红移,然后峰位不变且强度减弱。这一光致发光现象一方面可能与反应过程中部分银离子掺入Zn S纳米壳层有关;另一方面可能源于Ag2S中间层厚度的增加导致Zn S与Au的间距增加,从而导致Au对Zn S的等离子增强效果减弱。     

银负载细菌纤维素纳米复合材料的制备及抗菌性能研究

利用细菌纤维素超精细网络结构和高持水率的特点,在细菌纤维素上通过硼氢化钠(NaBH4)还原硝酸银中的Ag+原位生成纳米银颗粒,并对其微观结构等进行表征,同时对银负载细菌纤维素纳米复合膜的抗菌性能和生物相容性进行研究。XRD结果表明纳米银颗粒具有较完善的结晶结构,且银晶体为面心立方结构;XRF检测表明复合材料中含有Ag元素;由UV-Vis可知Ag/BC纳米复合材料在424nm处出现了Ag的吸收峰;从SEM图可看出随着硝酸银浓度的增大,细菌纤维素微纤表面负载的银颗粒增多,粒径大约为50～80nm。抗菌实验结果说明Ag/BC纳米复合材料具有很强的抗菌性能,对大肠杆菌和金黄色葡萄球菌的最大抑菌率分别达到99.4%和98.4%。细胞相容性实验表明,Ag/BC纳米复合材料还具有良好的细胞相容性。因此将其用于抗菌伤口敷料会有广阔的应用前景。     

日本开发新型电双层电容器

日本日立制作所和日立协和工程公司共同开发了一种新型无铅薄膜焊锡,用于光通讯器件的光学元件与基板的焊接,可以在比目前使用的Au—Sn合金薄膜焊锡的熔点（278℃）低40℃以上的较低温度下进行焊接。新型焊锡具有Sn／Ag／Au三层结构,可在232℃的低温下焊接,因此可防止焊锡表面氧化。由于可抑制因焊接温度导致的光学元件变形,因此可提高生产率。另外,由于不需进行影响光学元件性能的防氧化处理,使产品可靠性提高。     

贵金属纳米颗粒的表面等离子共振研究

通过修正的Mie理论分别对单金属Ag、单金属Cu和Cu核Ag壳纳米颗粒/玻璃复合材料的吸收光谱进行了理论计算.计算结果表明,对单金属Ag纳米颗粒/玻璃复合材料,Ag的吸收峰位于425nm左右,不随颗粒尺寸变化而发生偏移;对单金属Cu纳米颗粒/玻璃复合材料,Cu的吸收峰也不随尺寸变化发生偏移但强度较弱;对Cu核Ag壳纳米...     

Ag掺杂APS改性的TiO2颗粒的制备及其光催化降解作用

为提高Ag/TiO2纳米颗粒的光催化降解作用,采用聚合凝胶工艺路线,以钛酸四丁酯为前驱体,硝酸银为银源,通过向反应体系引入鳌合剂醋酸、表面改性剂γ-氨丙基三乙氧基硅烷(APS)以及还原剂甲醛等添加剂,制备出TiO2粉体及Ag/TiO2纳米复合粉体。利用FT-IR、XRD、TG-DTA、TEM和UV-Vis-NIR等手段对样品进行表征。结果表明,经γ-氨丙基三乙氧基硅烷改性的TiO2颗粒掺Ag后分散性得到改善,粒径约1 nm的Ag颗粒较均匀地分布在10～15 nm TiO2颗粒上;可见光的利用和锐钛矿热稳定性都得到提高;Ag/TiO2纳米颗粒在光照下对甲基橙具有良好的光催化降解效果。     

Ag-Cu离子注入SiO2玻璃后形成纳米颗粒的研究

Ag、Cu离子经200和110keV加速后分别以5×1016和1.5×1017ions /cm2的剂量在室温下先后注入到非晶SiO2玻璃中.注入后样品的光学吸收谱显示两个吸收峰,其峰位为407和569nm,分别对应单独Ag和单独Cu纳米颗粒的等离子体共振吸收峰,样品在还原-保护气氛下退火后吸收峰峰强明显增加.样品的透射电镜选区电子衍射花样含有Ag、Cu两套衍射环,透射电镜的明场像观察到大量的纳米颗粒呈现出中心亮斑特征.在样品倾转过程中,中心亮斑特征依然存在,证实这种现象是离子辐照产生的纳米空位团簇.扫描透射电子显微镜高角环形暗场像进一步证实了这一点.综上所述,样品中形成了单Ag和单Cu包裹空位团簇的纳米颗粒.     

脉冲激光液相烧蚀贵金属Au/Ag产物的表征及反应机理研究

采用多波长(1064nm、532nm、248nm)脉冲激光在去离子水中对责金属Au、Ag片表面进行激光烧蚀(PLA).利用TEM、AFM、SEM对烧蚀金属片表层及产物(微/纳米尺度的金属颗粒)进行观察分析,认为在液相水环境中,整个烧蚀过程主要可分为激光诱导相沸腾爆炸和等离子体羽辉混合体膨胀2个过程.在这2个过程中分别产生得到具有微米尺度的球状金属颗粒和纳米尺度的金属颗粒.同时,具有纳米尺度金属Au/Ag颗粒经过强激光光子"二次"修饰改性过程,形成具有形状统一、分散性和稳定性较好的金属纳米胶体体系,这些胶体中金属纳米颗粒作为探针,在表面增强拉曼散射(SERS)光谱学方面有很好的应用价值.     

Surface-enhanced Raman scattering dendritic substrates fabricated by deposition of gold and silver on silicon

This paper reports a study on the preparation of gold nanoparticles and silver dendrites on silicon substrates by immersion plating. Firstly, gold was deposited onto silicon wafer from HF aqueous solution containing HAuCl4. Then, the silicon wafer deposited gold was dipped into HF aqueous solution of AgNO3 to form silver coating gold film. Scanning electron microscopy reveals a uniform gold film consisted of gold nanoparticles and rough silver coating gold film containing uniform dendritic structures on silicon surface. By SERS (surface-enhanced Raman scattering) measurements, the fabricated gold and silver coating gold substrates activity toward SERS is assessed. The SERS spectra of crystal violet on the fabricated substrates reflect the different SERS activities on gold nanoparticles film and silver coating gold dendrites film. Compared with pure gold film on silicon, the film of silver coating gold dendrites film significantly increased the SERS intensity. As the fabrication process is very simple, cost-effective and reproducible, and the fabricated silver coating gold substrate is of excellent enhancement ability, spatial uniformity and good stability.     

有序Ag_(NW)@Au_(NP)复合纳米线的制备及其对聚(3-己基噻吩)荧光效应的影响

采用三相界面法及置换反应法,以氯金酸-乙醇溶液和无序Ag纳米线为原材料,在空白Si基底上成功制备出有序Ag纳米线(Ag_(NW))@Au纳米颗粒(Au_(NP))复合纳米线。采用场发射扫描电子显微镜(FESEM)和高分辨透射电子显微镜(HRTEM)对有序Ag_(NW)@Au_(NP)复合纳米线形貌进行了表征与分析,研究了氯金酸-乙醇溶液浓度和置换反应的反应时间对制备Ag_(NW)@Au_(NP)复合纳米线的影响,并且结合荧光光谱及激光拉曼光谱进一步研究了一系列有序Ag_(NW)@Au_(NP)复合纳米线对共轭聚合物聚(3-己基噻吩)(P3HT)荧光效应的影响。实验结果表明,有序Ag_(NW)@Au_(NP)复合纳米线上Au_(NP)的粒径随着置换反应时间的延长或氯金酸-乙醇溶液浓度的增加而增大,该复合纳米线对P3HT的荧光效应有增强作用,但其增强效应会随置换反应进行而减弱。     

Concentration effect on tuning of block copolymer-mediated synthesis of gold nanoparticles

Synthesis of gold nanoparticles has been examined using triblock copolymer Pluronic P85 (EO26PO39EO26) at different concentrations as a function of hydrogen tetrachloroaureate (III) hydrate (HAuCl4 x 3H2O) in aqueous solution. The concentration of P85 block copolymer was varied from 0.5 to 2 wt% at fixed temperature (30 degrees C) in presence of HAuCl4 x 3H2O in the range of 0.002 to 0.2 wt% for each P85 concentration. The surface plasmon resonance in the time-dependent UV-visible spectra reveals that increase in the block copolymer concentration increases the yield of the gold nanoparticles but decreases their stability. Both small-angle neutron scattering (SANS) and dynamic light scattering (DLS) show that the number density of block copolymer micelles increase almost linearly with the concentration, which is related to result in higher numbers of nucleation centers and therefore increase in the yield of gold nanoparticles. The fact that increase in the number density of nanoparticles also increases the chances of aggregation and this tends to decrease the stability at higher block copolymer concentration. Transmission electron microscopy (TEM) images confirm the larger sizes of the nanoparticles formed in these systems at higher concentrations.     

Fabrication of cubic nanocages and nanoframes by dealloying Au/Ag alloy nanoboxes with an aqueous etchant based on Fe(NO3)3 or NH4OH

This paper describes a two-step procedure for generating cubic nanocages and nanoframes. In the first step, Au/Ag alloy nanoboxes were synthesized through the galvanic replacement reaction between Ag nanocubes and an aqueous HAuCl4 solution. The second step involved the selective removal (or dealloying) of Ag from the alloy nanoboxes with an aqueous etchant based on Fe(NO3)3 or NH4OH. The use of a wet etchant other than HAuCl4 for the dealloying process allows one to better control the wall thickness and porosity of resultant nanocages because there is no concurrent deposition of Au. By increasing the amount of Fe(NO3)3 or NH4OH added to the dealloying process, nanoboxes derived from 50-nm Ag nanocubes could be converted into nanocages and then cubic nanoframes with surface plasmon resonance (SPR) peaks continuously shifted from the visible region to 1200 nm. It is also possible to obtain nanocages with relatively narrow SPR peaks (with a full width at half-maximum as small as 180 nm) by controlling the amount of HAuCl4 used for the galvanic replacement reaction and thus the optimization of the percentage of Au in the alloy nanoboxes.     

A facile preparative method for Au-core, block copolymer-shell nanoparticles by UV irradiation of polystyrene-block-poly (2-vinyl pyridine)/HAuCl4 solutions

The synthesis of gold nanoparticles (AuNPs) by UV irradiation of the solution of polystyrene-block-poly(2-vinyl pyridine)/HAuCl4 (PS-b-PVP/HAuCl4) complexes was investigated. AuNPs with block copolymer shell structures can be easily generated by simply control of the block copolymer concentration and the loading ratio of the HAuCl4 precursor. The cross-linked block copolymer shell structures were determined by transmission electron microscopy (TEM), contact angle measurement and thermogravimetic analysis (TGA). The obtained AuNPs with copolymer shells are stable in organic solvents and biochemical buffers.     

"Turn-on" chemiluminescence sensor for the highly selective and ultrasensitive detection of Hg2+ ions based on interstrand cooperative coordination and catalytic formation of gold nanoparticles

Monitoring the levels of potentially toxic metal ions such as Hg(2+) in aquatic ecosystems is important because this ion can have severe effects on human health and the environment. Thus, a novel chemiluminescence (CL) sensor is developed for the highly selective and ultrasensitive detection of Hg(2+) ions in aqueous solution, based on thymine-Hg(2+)-thymine (T-Hg(2+)-T) coordination chemistry and subsequent formation of gold nanoparticles (Au NPs) in a HAuCl(4)/NH(2)OH reaction. The thus-formed Au NPs trigger the reaction between luminol and AgNO(3), producing CL emission. This novel CL technique has several advantages including high sensitivity (0.01 ppb) and selectivity over a spectrum of interfering metal ions. In view of these advantages, as well as the cost-effective, minimized working steps and portable features of the CL techniques, we expect that this CL sensor will be a promising candidate for the field detection of toxic Hg(2+) ions in environment, water, and food samples.     

一种在硅材料表面组装金纳米颗粒的新方法

以氯金酸、L-半胱氨酸为反应试剂,利用内电流和金硫自组装效应,在硅材料表面组装了较为均一的金纳米颗粒,并利用荧光分析与硅纳米线场效应晶体管对该方法进行了相关验证.结果表明:经氢氟酸处理后的硅材料,在氯金酸和L_半胱氨酸混合溶液中反应3 min可在硅表面得到较为均匀、稳定的金纳米颗粒层,其中,氯金酸浓度为0.5mmol/L,氯金酸和L-半耽氨酸浓度比为3∶1.荧光分析表明该方法组装的金颗粒表面已氨基功能化,使得金纳米颗粒修饰的硅材料在应用于生物检测时可直接醛基化修饰蛋白,简化了实验操作,同时,该方法可以在硅纳米线场效应晶体管中特异性组装金纳米颗粒,有力地支持了相关器件在疾病检测方面的应用.     

Fabrication of silica nanocapsules containing Ag/Au alloy nanoparticles by galvanic replacement reaction

A straightforward method has been developed to generate silica nanocapsules containing Ag/Au alloy nanoparticles (Ag/Au@silica) by in-situ galvanic replacement reaction between the silica-coated silver (Ag@silica) nanoparticles with aqueous chloroauric acid (HAuCl4). Ag/Au@silica exhibits an optical absorbance derived from the surface Plasmon resonance of the encapsulated Ag/Au alloy nanoparticle. The behaviour of chemical diffusion across the silica shells of Ag/Au@silica is also investigated. It is worthy to noting that this facile synthetic strategy could be amenable to the other systems that involve the use of different combination of materials for the core (Pd/Ag, Pt/Ag alloy nanoparticles) and for the shell (titania).     

Green synthesis of highly stabilized nanocrystalline silver particles by a non-pathogenic and agriculturally important fungus T. asperellum

A controlled and up-scalable biosynthetic route to nanocrystalline silver particles with well-defined morphology using cell-free aqueous filtrate of a non-pathogenic and commercially viable biocontrol agent Trichoderma asperellum is being reported for the first time. A transparent solution of the cell-free filtrate of Trichoderma asperellum containing 1?mM AgNO(3) turns progressively dark brown within 5?d of incubation at 25?°C. The kinetics of the reaction was studied using UV-vis spectroscopy. An intense surface plasmon resonance band at ～410?nm in the UV-vis spectrum clearly reveals the formation of silver nanoparticles. The size of the silver particles using TEM and XRD studies is found to be in the range 13-18?nm. These nanoparticles are found to be highly stable and even after prolonged storage for over 6 months they do not show significant aggregation. A plausible mechanism behind the formation of silver nanoparticles and their stabilization via capping has been investigated using FTIR and surface-enhanced resonance Raman spectroscopy.     

Synthesis of complex shape gold nanoparticles in water-methanol mixtures

Gold nanoparticles with shapes which varied from spheres to multipods and polygons were prepared with a seedless approach in water/methanol mixtures in the presence of polyvinyl alcohol using sodium ascorbate as the reducing agent. The shape of Au nanoparticles is critically affected by the water/methanol ratio, as well as by the ratio of hydrogen tetrachloroaurate (HAuCl4) to sodium ascorbate and the concentration of HAuCl4 in the reaction mixture. A decreased ratio of water to methanol below 30/70 leads to the formation of multi-branched nanoparticles with the size in the range of 30-70 nm at relatively low HAuCl4 concentration, whereas polygons are formed when HAuCl4 concentration increases. The polyvinyl alcohol stabilized multi-branched Au nanoparticle colloids were stable at room temperature for a period of at least six-month.