聚乙烯吡咯烷酮辅助的水热法合成形貌可控的银纳米结构（英文）

以不同平均分子质量的聚乙烯吡咯烷酮(PVP,通常用K值来表示PVP溶液相对粘度的特征值,粘度越大,PVP平均分子质量越大,平均分子质量为8000、40000、160000、360000的PVP分别标记为K17、K30、K60、K90)为表面活性剂,通过水热法合成了形貌和光学共振峰可控的银纳米结构.将反应体系加入到60 mL的不锈钢高压反应釜中,在一定的温度下加热数小时.我们在K17的水溶液中合成了尺寸均一的五重孪晶银纳米十面体.而在K30、K60和K90的乙二醇(EG)溶液中得到了纵横比随着PVP分子质量增大而增大的银纳米线.产物的形貌和微结构通过透射电镜(TEM)和场发射扫描电镜(FE-SEM)进行表征,表面等离子共振(SPR)吸收峰通过紫外-可见分光光度计进行测试,结果显示银纳米结构的表面等离子共振随着其形貌和尺寸的改变而发生变化.     

溶剂热法制备银纳米晶

以聚乙烯吡咯烷酮(PVP)作为表面活性剂,利用乙二醇溶剂热法成功制备了银纳米颗粒;利用场发射扫描电子显微镜(FE-SEM)、透射电子显微镜(TEM)、X射线衍射(XRD)分析了样品的形貌和晶体结构,并考察了溶剂组成等因素对银纳米颗粒形貌的影响.研究结果表明所得银纳米晶粒径均一,直径约为90nm;增大PVP的加入量会降低产物的粒径,溶剂中水的引入会影响银纳米晶的形貌.     

帽状锑纳米粒子的制备及表面等离子共振特性的研究

采用热蒸发法在SiO₂自组装单层膜上制备了帽状锑纳米粒子,通过扫描电镜(SEM)、原子力显微镜(AFM)、X射线衍射仪(XRD)和紫外-可见-近红外(UV-Vis-NIR)分光光度计对帽状复合纳米粒子的表面形貌、结构以及表面等离子共振特性进行了研究和表征。结果表明,制备的复合纳米粒子呈帽状,表面等离子共振峰具有明显的可调谐性,当二氧化硅粒径增大或锑帽层厚度增加时,等离子共振吸收峰位置红移。     

帽状锡纳米粒子的制备及其表面等离子的共振特性

采用真空热蒸发法在SiO2自组装单层膜上沉积金属锡, 制备了帽状锡纳米结构, 通过扫描电镜(SEM)、原子力显微镜(AFM)、X射线衍射(XRD)仪和Cary 5000紫外-可见-近红外(UV-Vis-NIR)分光光度计对其表面形貌、结构以及光谱特性进行了研究和表征. 结果表明, 制备的复合纳米粒子呈帽状, 表面等离子共振峰位具有明显的可调谐性, 随二氧化硅粒径的增大或锡帽层厚度的增加, 表面等离子共振吸收峰向长波方向移动.     

边长为微米级的银纳米片的简易合成与形成机理

用低温(60 ℃)溶剂热法, 以N,N-二甲基甲酰胺(DMF)为主还原剂和溶剂, 以聚乙烯吡咯烷酮(PVP)为辅助还原剂和晶面生长控制剂, 以硝酸银为前驱物, 大量制备了高纯度的、边长为微米级、宽厚比≥10的单晶银纳米片. 采用粉末X射线衍射(PXRD)、场发射扫描电镜(FE-SEM)、透射电子显微镜(TEM)等表征和分析了合成产物的成分、形貌和结构. 结果表明, 合成的银纳米片为面心立方单晶, 边长为1-4 μm, 厚度为50-100 nm. 考察了不同溶剂对银纳米结构的影响, 并提出了大尺寸的银纳米片的形成机理. 本文为调控单晶银纳米片的边长和宽厚比提供了一种新的可靠的动力学方法, 制备的长边长、大宽厚比的单晶银纳米片在聚合物基导电复合材料和电磁屏蔽材料方面有潜在的重要应用.     

边长为微米级的银纳米片的简易合成与形成机理眄

用低温(60℃)溶剂热法,以N,N-二甲基甲酰胺(DMF)为主还原剂和溶剂,以聚乙烯吡咯烷酮(PVP)为辅助还原剂和晶面牛长控制剂,以硝酸银为前驱物,大量制备r高纯度的、边长为微米级、宽厚比≥10的单晶银纳米片.采用粉末X射线衍射(PXRD)、场发射扫描电镜(FE-SEM)、透射电子显微镜(TEM)等表征和分析了合成产物的成分、形貌和结构.结果表明,合成的银纳米片为面心立方单晶,边长为1-4μm,厚度为50-100nm.考察了不同溶剂对银纳米结构的影响,并提出了大尺寸的银纳米片的形成机理.本文为调控单晶银纳米片的边长和宽厚比提供了一种新的可靠的动力学方法,制备的长边长、大宽厚比的单晶银纳米片在聚合物基导电复合材料和电磁屏蔽材料方面有潜在的重要应用.     

银纳米棱镜的形成及其光学性能研究

以有机溶剂作为反应介质,聚合物为稳定剂,通过微波辅助溶液法成功地制备了具有特殊光学性能的银纳米棱镜.利用X射线衍射、透射电子显微镜和紫外-可见光谱等手段跟踪反应过程.结果显示,随着反应的进行,银纳米粒子由10nm左右的球形颗粒逐渐转变为具有规则三角形(或缺角的三角形)形貌的纳米棱镜;同时,紫外-可见吸收峰不但显示出明显的量子尺寸效应,而且吸收峰也由单一的等离子共振吸收峰变为多重的多极吸收峰共同存在,胶体溶液也随之显示出不同的颜色.改变反应物的配比、体系的浓度及无机前驱物都会得到位置和峰形各不相同的吸收曲线,从而得到多彩的纳米银胶体溶液.     

银/铂双金属中空纳米颗粒的制备及光学性质研究

通过以Ag纳米颗粒为模板的置换和沉积反应,制备了Ag/Pt双金属复合纳米颗粒.用透射电子显微镜(TEM)对颗粒的形貌、尺寸和结构进行了表征,发现复合颗粒具有中空结构.紫外可见吸收光谱(UV-Vis)研究表明,Ag/Pt双金属中空复合纳米颗粒具有单峰的表面等离子共振吸收特征,随着反应溶液中氯铂酸和硝酸银摩尔比的增加,吸收峰先红移后蓝移.表面增强拉曼光谱实验结果表明,Ag/Pt双金属复合纳米颗粒对吡啶分子具有较好的增强效果.     

Microwave synthesis of silver nanofluids with polyvinylpyrrolidone (PVP) and their transport properties

Microwave synthesis has been applied to prepare stable silver nanofluids in ethanol by reduction of AgNO₃ with polyvinylpyrrolidone (PVP), used as stabilizing agent, having Ag concentrations of 1% by volume. The nanofluids were characterized by UV-vis spectroscopy, Fourier transform infrared, energy-dispersive X-ray spectroscopy, and transmission electron microscopy and systematically investigated for refractive index, electrical and thermal conductivity, and viscosity for different polymer concentrations. The size of nanoparticles was found to be in the range of 30–60 nm for two different salt-to-PVP ratios. For higher concentration of polymer in nanofluid, nanoparticles were 30 nm in size showing increase in thermal conductivity but a decrease in viscosity and refractive index, which is due to the polymer structure around nanoparticles. Thermal conductivity measurements of nanofluids show substantial increment in the thermal conductivity of nanofluid relative to the base fluid and nonlinear enhancement over the 283–323 K temperature range. Rheology of nanofluids was studied at room temperature showing effect of polymer on viscosity and confirming the Newtonian behavior of nanofluid.     

银纳米晶体的制备与表征

在聚乙烯吡咯烷酮存在的条件下,用水合肼还原硝酸银,通过控制反应条件成功制备出了粒径均一、有良好分散性的银纳米微粒,并以此为种子,利用种子诱导生长,在十六烷基三甲基溴化铵的棒状胶束环境中制备出了银纳米棒和纳米线.并用X射线衍射、透射电子显微镜、傅立叶红外光谱和紫外-可见光谱等手段对产品的形貌、结构进行了表征.     

Self-assembly and branching of sucrose stabilized silver nanoparticles by microwave assisted synthesis: From nanoparticles to branched nanowires structures

Silver nanostructures were synthesized under microwave irradiation from a solution of silver nitrate and sucrose, with any other reducing or capping agent. The size and morphology of nanostructures changed continuously during the irradiation time. The obtained nanostructures at the different irradiation time were characterized by X-Ray diffraction, UV–vis spectroscopy, scanning and transmission electron microscopy and selected area diffraction pattern. It was evidenced that initially Ag nanoparticles were formed, which, as reaction time elapsed, self-assembled and fused with each other to yield nanowires and further branched nanowires. The formation of the silver branched nanostructures can be explained as a process of initial reduction–nucleation–adsorption–growth–branching growth.     

Structural and optical characteristics of silver/poly(N-vinyl-2-pyrrolidone) nanosystems synthesized by γ-irradiation

Silver nanoparticles (AgNPs) were synthesized in situ by γ-irradiation using poly(N-vinyl-2-pyrrolidone) (PVP) as a capping agent. The concentration, molecular weight and the structure (crosslinked and interpenetrated network) of PVP were varied, in order to determine the influence of the capping agent in the radiolytic synthesis of the Ag/PVP nanosystems. Transmission electron microscopy (TEM) showed that AgNPs obtained from the solutions containing higher PVP concentration and higher molecular weight were spherical in shape, with narrow size distribution and a diameter of～6 nm, while slightly larger rod-shaped silver agglomerates, with bimodal nanoparticle size distribution and diameters of ～10 nm and ～20 nm were obtained from the solutions containing lower PVP concentration and lower molecular weight. Strong plasmon coupling and extending of plasmon resonance was observed by UV–vis spectroscopy, as a result of formation of nanorod-like agglomerates. Crosslinked and interpenetrated network did not affect the structure of synthesized AgNPs. Ag/PVP nanocomposite, in the form of thin film, was obtained by solvent evaporation from Ag/PVP colloid solution with 10 wt% of PVP, and characterized by FTIR spectroscopy. The interactions in Ag/PVP nanocomposite are shown to be the result of the coordination bonding between AgNPs and nitrogen from pyrrolidone ring of PVP. The optical properties of investigated Ag/PVP nanosystems, as measured by the values of optical band gap, E_g, are mainly the consequence of the interparticle distance as a result of the concentration and the structure of surrounding PVP macromolecules.     

Rapid transformation from spherical nanoparticles, nanorods, cubes, or bipyramids to triangular prisms of silver with PVP, citrate, and H2O2

Rapid sphere-to-prism (STP) transformation of silver was studied in aqueous AgNO(3)/NaBH(4)/polyvinylpyrrolidone (PVP)/trisodium citrate (Na(3)CA)/H(2)O(2) solutions by monitoring time-dependent surface plasmon resonance (SPR) bands in the UV-vis region, by examining transmission electron microscopic (TEM) images, and by analyzing emitted gases during fast reaction. Roles of PVP, Na(3)CA, and H(2)O(2) were studied without addition of a reagent, with different timing of each reagent's addition, and with addition of H(2)O(2) to mixtures of spheres and prisms. Results show that prisms can be prepared without addition of PVP, although it is useful to synthesize smaller monodispersed prisms. A new important role of citrate found in this study, besides a known role as a protecting agent of {111} facets of plates, is an assistive agent for shape-selective oxidative etching of Ag nanoparticles by H(2)O(2). The covering of Ag nanoparticles with carboxylate groups is necessary to initiate rapid STP transformation by premixing citrate before H(2)O(2) addition. Based on our data, rapid prism formation starts from the consumption of spherical Ag particles because of shape-selective oxidative etching by H(2)O(2). Oxidative etching of spherical particles by H(2)O(2) is faster than that of prisms. Therefore, spherical particles are selectively etched and dissolved, leaving only seeds of prisms to grow into triangular prisms. When pentagonal Ag nanorods and a mixture of cubes and bipyramids were used as sources of prisms, rod-to-prism (RTP), cube-to-prism (CTP), and bipyramid-to-prism (BTP) transformations were observed in Ag nanocrystals/NaBH(4)/PVP/Na(3)CA/H(2)O(2) solutions. Shape-selective oxidative etching of rods was confirmed using flag-type Ag nanostructures consisting of a triangular plate and a side rod. These data provide useful information for the size-controlled synthesis of triangular Ag prisms, from various Ag nanostructures and using a chemical reduction method, having surface plasmon resonance (SPR) bands at a desired wavelength.     

Differential SERS activity of gold and silver nanostructures enabled by adsorbed poly(vinylpyrrolidone)

We report that poly(vinylpyrrolidone) (PVP), a common stabilizer of colloidal dispersions of noble metal nanostructures, has a dramatic effect on their surface-enhanced Raman scattering (SERS) activity and enables highly selective SERS detection of analytes of various type and charge. Nanostructures studied include PVP-stabilized Au-Ag nanoshells synthesized by galvanic exchange reaction of citrate-reduced Ag nanoparticles (NPs), as well as solid citrate-reduced Ag and Au NPs, both before and after stabilization with PVP. All nanostructures were characterized in terms of their size, surface plasmon resonance wavelength, surface charge, and chemical composition. While the SERS activities of the parent citrate-reduced Ag and Au NPs are similar for rhodamine 6G (R6G) and 1,2-bis(4-pyridyl)ethylene (BPE) at various pH values, PVP-stabilized nanostructures demonstrate large differences in SERS enhancement factors (EFs) between these analytes depending on their chemical nature and protonation state. At pH values higher than BPE's pK(a2) of 5.65, where the analyte is largely unprotonated, the PVP-coated Au-Ag nanoshells showed a high SERS EF of >10(8). In contrast, SERS EFs were 10(3)- to 10(5)-fold lower for the protonated form of BPE at lower pH values, or for the usually highly SERS-active cationic R6G. The differential SERS activity of PVP-stabilized nanostructures is a result of discriminatory binding of analytes within-adsorbed PVP monolayer and a subsequent increase of analyte concentration at the nanostructure surface. Our experimental and theoretical quantum chemical calculations show that BPE binding with PVP-stabilized Au-Ag nanoshells is stronger when the analyte is in its unprotonated form as compared to its cationic, protonated form at a lower pH.     

Electrochemical synthesis of gold nanocrystals and their 1D and 2D organization

Size-controlled gold nanocrystals were conveniently synthesized through direct electroreduction of bulk AuCl(4)(-) ions in the presence of poly(N-vinylpyrrolidone) (PVP). PVP greatly enhanced the gold particle formation process and also significantly retarded the gold electrodeposition process, allowing the electrochemical synthesis of gold nanocrystals to be carried out in the form of simple electroreduction. This novel electrochemical method may be extended to synthesis of other noble metal nanoparticles with controllable size on a large scale. The PVPK90-protected gold nanocrystals spontaneously self-assembled into nearly ordered 2D close-packed arrays and interesting 1D nanostructures. The aggregation of unstable PVPK17-protected gold nanocrystals resulted in the formation of ultrathin single-crystalline films. PVP plays multifunctional roles in controlling the size and shape of gold nanocrystals and in inducing individual gold nanocrystals to construct 1D nanostructures. The nanoparticle self-assembling technique based on PVP offers a simple, but effective, path to organize individual gold nanoparticles into various 1D and 2D nanostructured materials.     

Assembly and characterization of Ag nanoparticles in PAM-g-PVA/PVP semi-interpenetrating network hydrogels

Polyacrylamide grafted poly(vinyl alcohol)/polyvinylpyrrolidone (PAM-g-PVA/PVP) semi-interpenetrating network (semi-IPN) hydrogels were designed and prepared via a simple free radical polymerization reaction process initiated by a PVA-(NH₄)₂Ce(NO₃)₆ redox system. The structure of the PAM-g-PVA/PVP semi-IPNs was characterized by a Fourier transform infrared spectroscopy. The morphologies of PAM-g-PVA/PVP hydrogels and PAM-g-PVA/PVP/Ag nanocomposite hydrogels were examined by scanning electron microscopy and transmission electron microscopy (TEM). The experimental results indicated that the PAM, PVA or PVP chains can efficiently act as stabilizing agents for Ag nanoparticles. TEM investigation of sample morphology showed the presence of nearly spherical-, square- or rectangular-shaped Ag nanoparticles with diameters ranging from 10 to 60 nm. The characteristic surface plasmon resonance band appeared at 390–400 run as a result of the immobilization of Ag nanoparticles within the hydrogel matrices. The self-assembly of Ag nanoparticles and the swelling behavior of the resulting nanocomposites can be controlled and modulated by altering the mole fraction of PVP in the PAM-g-PVA/PVP semi-IPNs.     

多羟基化合物法制备五次孪晶银纳米线的生长机理

运用多羟基化合物方法, 在添加表面活性剂聚乙烯吡咯烷酮(PVP) K30的溶液中合成了多次孪晶银纳米颗粒和纳米线. 运用透射电子显微术(TEM)和光吸收谱, 对不同的摩尔比n(PVP):n(AgNO3)和不同的搅拌条件下制备的纳米线进行了对比研究. 结果表明, 这种方法的制备过程中不仅存在由五个{111}面包裹成的锥形生长, 而且还同时存在垂直于生长方向的{110}层状生长, 并且两者之间还存在着竞争; 另外对纳米线的弯折处进行的高分辨电子显微学研究表明, 纳米线制备过程中遭受的塑性变形在纳米线中产生了大量的层错和位错; 纳米线折断产生的新鲜断口容易成为新的晶粒形核位置.     

High-quality luminescent tellurium nanowires of several nanometers in diameter and high aspect ratio synthesized by a poly (vinyl pyrrolidone)-assisted hydrothermal process

Large-scale selective synthesis of uniform single crystalline tellurium nanowires with a diameter of 4-9 nm, and microbelts with a width of 250-800 nm and tens of micrometers in length, can be realized by a poly (vinyl pyrrolidone) (PVP)-assisted hydrothermal process. The formation of tellurium nanowires and nanobelts in the presence of PVP is strongly dependent on the reaction conditions such as temperature, the amount of PVP, and reaction time. The results demonstrated that the keys for selective synthesis of Te nanobelts and nanowires are to modulate the growth rates of (100), (101), and (110) planes in the presence of PVP and to precisely control the reaction kinetics. High-quality luminescent ultrathin t-Te nanowires with a diameter of 4-9 nm display strong luminescent emission in the blue-violet region. This approach provides a facile route for the production of high-quality tellurium nanostructures with an interesting optical property. Furthermore, the synthesized ultrathin nanowires with deep blue color and nanobelts in gray color by this approach can be well dispersed in water or ethanol, making it possible for further engineering of their surfaces to prepare other hybrid core-shell nanostructures.