单分散、小粒径金纳米颗粒的形貌控制增长

利用种子生长法合成了形状规则、尺寸单一的形状不同金纳米颗粒. 其中立方体纳米颗粒的边长为33±2 nm, 它是在十六烷基三甲基溴化胺(CTAB)存在的条件下, 在种子的表面上用弱还原剂——抗坏血酸还原而成的. 在这个体系中, 表面活性剂CTAB既作为保护剂又作为颗粒成长的导向剂. 用UV-vis, TEM, XRD对纳米颗粒的光学性质、几何形状、纳米颗粒的单层膜概貌以及纳米颗粒的晶体结构作了表征. 考察了种子生长的时间、种子的量、抗坏血酸的量对生成纳米颗粒形状的影响.     

在SDS-PVP团簇软模板中自组装多脚状金纳米粒子

利用十二烷基硫酸钠(SDS)与聚乙烯吡咯烷酮(PVP)组成的团簇为软模板, 在微波辅助下以柠檬酸钠为还原剂快速还原氯金酸生成金晶并自组装成多脚状金纳米粒子. TEM结果显示, 得到回转直径约为50 nm的多脚状纳米结构, 电子衍射(ED)证实其为多晶结构. XRD结果表明, 该多脚状金纳米结构主要沿(111)晶面生长, 构成该纳米结构的晶粒尺寸约为12.7 nm. SDS与PVP组成的团簇结构对金纳米粒子的形貌有显著影响, 固定PVP浓度时, 随着SDS浓度增大, 金纳米粒子的形貌由球形向多脚状转变, 同时还原产物水溶液的UV-Vis光谱在800 nm附近的吸收逐渐增强.     

微波法合成纳米金胶体颗粒的调控研究

用微波法制备高分子聚合物稳定的纳米金胶体颗粒, 制得的金纳米颗粒的平均粒径在5～120 nm之间. 考察了醇还原剂以及碱对金颗粒形成的影响, 使用透射电子显微镜、紫外可见分光光度计进行表征. 结果表明, 微波法制备的金胶体颗粒具有粒径小、分散性好的特点. 金颗粒的尺寸和形状随醇还原剂的种类及碱(NaOH)用量的不同而有明显的变化. 紫外可见吸收光谱表明, 在反应物中加入碱的体系, 金颗粒的形成速度明显加快, 且利于圆球形金颗粒的形成.     

山竹果壳提取液中金纳米粒子的生物合成及光谱性质研究

在山竹果壳提取液中,以山竹多酚既作还原剂又作保护剂,制备了具有高度稳定性、单分散性的亲水性金纳米粒子。利用紫外可见分光光度法、透射电子显微镜和X射线衍射等手段对制备的金纳米粒子进行了表征和分析。结果表明:金纳米粒子的尺寸大小在9~23nm范围,升高温度其还原反应速率加快,所得金纳米粒子的尺寸减小、单分散性提高。山竹多酚保护金的金纳米颗粒具有pH值调控的分散可逆性。降低山竹提取液的浓度可得到包括单晶纳米片在内的多形态金纳米颗粒。     

纳米金-钛酸纳米管复合材料的合成与表征

以氯金酸和钛酸钠米管(NTA)为原料,柠檬酸三钠为稳定剂,硼氢化钠为还原剂,于室温条件下合成了一种金纳米颗粒-钛酸纳米管(GNPs-NTA)复合纳米材料;利用红外光谱仪、透射电镜、X射线粉末衍射仪等分析了产物的化学键合特征、微结构及相组成,并考察了产物对辣根过氧化酶(HRP)结构和生理活性的影响.结果表明,合成的纳米金颗粒粒径(平均5.3nm)分布窄,且均匀分布于钛酸纳米管表面.此外,HRP与GNPs-NTA复合纳米材料充分振荡混合后仍能保持其二级结构不变,有利于保持其生理活性.     

紫外光辐照法制备金纳米盘及其反应机理

用紫外光辐照氯金酸、聚乙烯吡咯烷酮(PVP)和纳米金种子的混合溶液, 在室温下用30 min制备出尺度小于100 nm的截角三角形或六边形金纳米盘. X射线能谱和衍射分析表明粒子是以{111}面为盘状面的高纯面心立方金单晶, 红外透射光谱表明金粒子与PVP之间存在作用. 产物的可见吸收光谱表现出纳米盘的各向异性表面等离子体共振吸收峰. 不同实验条件下产物的吸收光谱分析表明: PVP起还原剂和包覆剂的作用; 高强度紫外光加速了反应进行; 种子对反应具有催化作用; 种子的加入量有最佳值, 在该值下纳米盘平均尺度最大(达80 nm), 吸收谱上的面内偶极共振峰位于950 nm处; 种子的加入量超过该值时, 纳米盘尺度变小, 面内偶极共振峰发生蓝移.     

反相微乳液中憎水性纳米金的原位还原法合成

利用十八胺(C18NH2)/正丁醇/正庚烷/HAuCl4(aq)W/O型微乳液体系,在常温的碱促进条件下由正丁醇原位还原氯金酸合成了具有高度单分散的憎水性金纳米粒子。由C18NH2稳定的金纳米颗粒运用紫外可见光谱(UV-vis)、透射电镜(TEM)和X射线衍射(XRD)等分别进行了表征和分析,并探讨了微乳液体系各组分对形成金纳米粒子形貌、尺寸和单分散性的影响。结果显示,随十八胺/氯金酸摩尔比的增加,金粒子的尺寸逐渐减小而单分散性逐渐提高。在正丁醇原位慢还原氯金酸的过程中,实验所选W/O型微乳液模板和表面活性剂十八胺分子对憎水性金纳米粒子的形貌和尺寸仍具有良好的控制作用。     

壳聚糖修饰的Pt纳米粒子

以氯铂酸为前驱体,硼氢化钠为还原剂,壳聚糖为保护剂,通过化学还原法,在室温条件下制备了Pt纳米粒子.透射电镜(TEM)显示纳米粒子的粒径在28.5nm左右,X-射线衍射(XRD)表明纳米粒子的晶型为面心立方结构,X-光电子能谱(XPS)和红外(FTIR)证实了壳聚糖包覆在纳米粒子表面,热重分析(TGA)表明纳米粒子表面的壳聚糖含量大约为52.8％.     

聚乙烯吡咯烷酮碱性水溶液中金纳米花的简易合成

以聚乙烯吡咯烷酮(PVP)兼作保护剂和还原剂在碱性水溶液中直接还原HAuCl₄制备出了60-80 nm的三维(3D)金纳米花. 产物的透射电子显微镜(TEM)和扫描电子显微镜(SEM)图像显示, 金纳米花表面布满10-15 nm左右的纳米触角, X射线衍射(XRD)表征揭示产物为金的面心立方晶体, 选区电子衍射(SAED)花样说明金纳米花为多晶结构. 金纳米花的生长经历了三个关键步骤, 即初级纳米晶聚集成多脚状纳米粒子, 随后在合适的PVP/HAuCl₄浓度比及NaOH浓度下, 多脚状纳米粒子进一步聚集形成疏松的花状粒子, 最终经过Ostwald熟化形成致密的花状产物. 一定HAuCl₄浓度下PVP/HAuCl₄浓度比和NaOH浓度对产物的形貌影响显著, 因此通过同时调控合适的PVP/HAuCl₄浓度比和NaOH浓度, 就能得到适应各种应用需求的尺度可控和纳米触角形貌可控的金纳米花.     

微波辅助4-十二烷氧基苄胺保护的憎水性纳米金原位还原合成

利用新型表面活性剂4-十二烷氧基苄胺(C₁₂OBA)构成的C₁₂OBA/正庚烷/正丁醇/HAuCl₄/NaOH(aq.) W/O型微乳液作为微反应器, 通过微波辐射加热的正丁醇原位还原法制备了C₁₂OBA包裹的憎水性金纳米粒子, 并通过紫外可见光谱(UV-vis)、透射电镜(TEM)、X射线衍射(XRD)、红外光谱(FT-IR)和接触角(CA)等分别进行了表征和分析. 结果显示, C₁₂OBA既可参与形成稳定的W/O型微乳液, 又可作为金粒子的良好保护剂. 微乳液内核中碱度的增加能增强位于膜相的正丁醇分子的还原能力. 在固定氯金酸用量时, C₁₂OBA/金的物质的量比增加有利于获得小尺寸、高单分散性的憎水性纳米金颗粒, 而体系的极性增加则导致金粒子的尺寸增大、单分散性下降. 通过本实验方法可方便快速地合成尺寸约为5 nm的具有高度单分散的憎水性金纳米粒子.     

Mechanistic study of the synthesis of Au nanotadpoles, nanokites, and microplates by reducing aqueous HAuCl4 with poly(vinyl pyrrolidone)

This article describes a simple approach to anisotropic Au nanostructures with various shapes by reducing HAuCl 4 with poly(vinyl pyrrolidone) (PVP) in aqueous solutions without the use of any additional capping agent or reductant. In this approach, the commercially available PVP servers as a mild reducing agent thanks to its hydroxyl (-OH) end groups, enabling kinetic control over both nucleation and growth. As the volume of HAuCl 4 solution added to the reaction was increased, the morphology of Au nanostructures evolved from nanotadpoles to nanokites and then triangular and hexagonal microplates. The slow reduction rate associated with the mild reducing power of PVP plays a critical role in forming nanoplates during nucleation as well as their growth into highly anisotropic nanostructures. Electron microscopy studies reveal that the nanotadpoles and nanokites are formed through the linear fusion of small Au particles (<10 nm) to the initially formed nanoplates, whereas the microplates result from the continuous addition of Au atoms to the side faces of nanoplates. Through this morphological control, the localized surface plasmon resonance peaks of these Au nanostructures can be tuned in the visible and near-IR regions.     

Poly(N-vinyl-2-pyrrolidone) (PVP)-capped dendritic gold nanoparticles by a one-step hydrothermal route and their high SERS effect

Dendritic gold (Au) nanoparticles have been successfully synthesized by the one-step hydrothermal reduction of HAuCl4.4H2O using ammonium formate (AF) as a reducing agent in the presence of PVP. Effects of different reactant concentrations on the morphologies of obtained products have been systematically investigated. On the basis of the morphologies of the products observed by transmission electron microscopy (TEM) and scanning electron microscopy (SEM), it has been found that an excessive number of AF molecules are the origin of the dendritic Au particles besides PVP as a stabilizer. AF molecules serve not only as a reductant but probably also as a capping reagent. The study implies that the use of two or more capping reagents with different adsorption abilities will be beneficial to the formation of hyperbranched Au nanoparticles. The new finding will have the potential to be extended to the construction of other highly branched noble metal nanoparticles only by one-step synthesis. In addition, as an example, application of the dendritic particles as an active material in surface-enhanced Raman scattering has been investigated by employing 4-aminothiophenol molecules as a probe.     

Seed‐Mediated Synthesis of Single‐Crystal Gold Nanospheres with Controlled Diameters in the Range 5–30 nm and their Self‐Assembly upon Dilution

Single‐crystal gold nanospheres with controlled diameters in the range 5–30 nm were synthesized by using a facile approach that was based on successive seed‐mediated growth. The key to the success of this synthesis was the use of hexadecyltrimethylammonium chloride (CTAC) as a capping agent and a large excess of ascorbic acid as a reductant to ensure fast reduction and, thus, single crystallinity and a spherical shape of the resultant nanoparticles. The diameters of the gold nanospheres could be readily controlled by varying the amount of seeds that were introduced into the reaction system. The gold nanospheres could be produced with uniform diameters of up to 30 nm; thus, their localized surface plasmon resonance properties could be directly compared with the results that were obtained from theoretical calculations. Interestingly, we also found that these gold nanospheres self‐assembled into dimers, larger aggregates, and wavy nanowires when they were collected by centrifugation, dispersed in deionized water, and then diluted to different volumes with deionized water.     

Poly(vinyl pyrrolidone): a dual functional reductant and stabilizer for the facile synthesis of noble metal nanoplates in aqueous solutions

Poly(vinyl pyrrolidone) (PVP) has been extensively used in the solution-phase synthesis of many types of colloidal particles, where it is mainly considered as a steric stabilizer or capping agent with a major role to protect the product from agglomeration. In a recent study, we discovered that the hydroxyl end groups of PVP could also serve as a very mild reductant for kinetically controlled synthesis of Ag nanoplates with yields as high as 75%. Here we further demonstrate that hydroxyl-terminated PVP is also a well-suited reductant for the aqueous synthesis of circular, triangular, and hexagonal nanoplates made of other noble metals including Pd, Au, and Pt. The reduction kinetics of a metal salt by the hydroxyl end groups of PVP can be maneuvered in at least two different ways to facilitate the evolution of plate morphology: (i) by adjusting the molar ratio of PVP to the salt precursor and (ii) by altering the molecular weight of PVP. Unlike previously reported studies of Ag and Au thin plates, light was found to have a negligible role in the present synthesis.     

Controlling the Size and Morphology of Au@Pd Core–Shell Nanocrystals by Manipulating the Kinetics of Seeded Growth

This article reports a systematic study of the seed‐mediated growth of Au@Pd core–shell nanocrystals with a variety of controlled sizes and morphologies. The key to the success of this synthesis is to manipulate the reaction kinetics by tuning a set of reaction parameters, including the type and concentration of capping agent, the amount of ascorbic acid used as the reducing agent, and the injection rate used for the precursor solution. Starting from Au nanospheres of 11 nm in diameter as the seeds, Au@Pd core–shell nanocrystals with a number of morphologies, including octahedra, concave octahedra, rectangular bars, cubes, concave cubes, and dendrites, could all be obtained by simply altering the reaction rate. For the first time, it was possible to generate Au@Pd nanocrystals with concave structures on the surfaces while their sizes were kept below 20 nm. In addition, the as‐prepared Au@Pd nanocubes can be used as seeds to generate Au@Pd@Au and Au@Pd@Au@Pd nanocrystals with multishelled structures.     

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...     

Controlling the size and morphology of Au@Pd core-shell nanocrystals by manipulating the kinetics of seeded growth

This article reports a systematic study of the seed-mediated growth of Au@Pd core-shell nanocrystals with a variety of controlled sizes and morphologies. The key to the success of this synthesis is to manipulate the reaction kinetics by tuning a set of reaction parameters, including the type and concentration of capping agent, the amount of ascorbic acid used as the reducing agent, and the injection rate used for the precursor solution. Starting from Au nanospheres of 11?nm in diameter as the seeds, Au@Pd core-shell nanocrystals with a number of morphologies, including octahedra, concave octahedra, rectangular bars, cubes, concave cubes, and dendrites, could all be obtained by simply altering the reaction rate. For the first time, it was possible to generate Au@Pd nanocrystals with concave structures on the surfaces while their sizes were kept below 20?nm. In addition, the as-prepared Au@Pd nanocubes can be used as seeds to generate Au@Pd@Au and Au@Pd@Au@Pd nanocrystals with multishelled structures.     

Synthesis of branched gold nanocrystals by a seeding growth approach

Synthesis of branched gold nanocrystals by a seeding growth approach is described. In this process, HAuCl4 aqueous solution was supplied stepwise to grow the gold seeds (approximately 2.5 nm) into larger nanoparticles with a highly faceted particle structure (approximately 15-20 nm in diameter). Sodium dodecyl sulfate (SDS) served as a capping agent to facilitate the formation of highly faceted nanoparticles, and ascorbic acid was used as a weak reducing agent. The highly faceted nanoparticles then transformed into branched nanocrystals (approximately 40 nm in length) by further addition of the SDS-HAuCl4 solution and ascorbic acid for particle growth. The branched nanocrystals show bipod, tripod, tetrapod, and pentapod structures and are composed of mainly (111) lattice planes. These multipods appear to grow along the twin boundaries of the initially formed highly faceted gold nanoparticles, as the twin boundaries on the pods originate from the centers of the branched nanocrystals. The concentration of ascorbate ions in the solution was found to have a profound influence on branch formation. These branched nanocrystals are stable to storage at low temperature (that is, 4 degrees C), but they may slowly evolve into a multitwinned faceted crystal structure (that is, pentagonal-shaped decahedral structure) when stored at 30 degrees C.     

Fabrication of flower-like silver nanoparticles for surface-enhanced Raman scattering

The flower-like silver nanoparticles have been synthesized by reducing silver nitrate (AgNO₃) with ascorbic acid (AA) as the reductant and polyvinyl pyrrolidone (PVP) as the capping agent under vigorous stirring. Such flower-like nanoparticles are aggregates of small nanoplates and nanorods. They were tested as substrates for the surface-enhanced Raman scattering (SERS), showing high sensitivity for detecting Rhodamine 6G (R6G) at a concentration as low as 10^-7 mol/L. It has been found that replacing mechanical stirring with ultrasound sonication would drastically change the particle morphology, from flower-like nanoparticles to well-dispersed smaller nanoparticles. Furthermore, when trace amounts of NaCl were added into the reagents, well-dispersed Ag nanoparticles formed even in vigorous stirring. These phenomena can be explained with the diffusion and reactant supply during nucleation and growth of Ag nanoparticles.