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.     

银纳米片的研究进展

金属纳米材料具有不同于宏观块体材料的特殊性质. 在银纳米结构中, 银纳米片因其独特的形貌依赖光学性质备受关注, 该特性已在离子检测、分子染色、表面增强拉曼光谱(SERS)、表面荧光增强、生物医学等领域显示了重要应用价值. 本文从银纳米片的制备方法入手, 首先综述了银纳米片的各种制备方法以及实验条件(如光照的波长、表面活性剂种类、还原剂种类)对产物形貌的影响. 其次介绍了银纳米片的奇特光学性质, 总结了银纳米片的几种重要生长机制, 最后介绍了银纳米片的应用价值, 并对银纳米片的研究前景做了展望.     

以SDS-PEG团簇为软模板在温和条件下合成金纳米环

介绍一种由十二烷基硫酸钠(SDS)与聚乙二醇(PEG 20000)组成的团簇为软模板, 在室温、常压、无硬模板及无外加还原剂条件下自还原HAuCl₄合成金纳米环的新方法. TEM显示合成的金纳米环的直径为(500±50) nm; UV-vis光谱显示在800 nm以上区域有强吸收带, 证明有大的各向异性的纳米结构生成. 电子衍射(ED)显示合成的金纳米环为金单晶结构; XRD显示金纳米环的(200)与(111)衍射峰的强度比(I₍₂₀₀₎/I₍₁₁₁₎)为0.11, 比反应初始阶段的0.31降低0.2左右, 表明金纳米结构主要为(111)晶面取向. TEM和SEM跟踪显示, 金纳米环的生长经历了从金纳米球到纳米片再到纳米环的变化过程, 控制反应时间可以得到预期的金纳米结构.     

烟草花叶病毒介导合成三角形金纳米片

利用碱处理烟草花叶病毒的生物还原性和辅助结构导向作用,在室温下以水为溶剂直接还原氯金酸制备出三角形金纳米片。采取透射电子显微镜（TEM）、高分辨透射电子显微镜（HRTEM）、选区电子衍射（SAED）和紫外-可见光谱仪（UV-Vis）等对所制备金纳米片的结构和性能进行了表征。结果显示,所制备三角形金纳米片为单晶,三角面为{111}晶面簇,边长在40 ~120 nm之间,厚度约为15 nm。该材料在可见光区有两个等离子共振吸收峰,在感光成像、生物检测和催化等领域具有很好的应用前景。     

儿茶素-银纳米复合材料的制备及其应用

探索了以植物活性成分儿茶素作为还原剂和保护剂一步水热法合成儿茶素-银纳米复合材料,并进一步测试了纳米复合材料的抑菌活性。 紫外可见吸收光谱(UV-Vis)和红外光谱(FTIR)测定证明制备得到了儿茶素包裹的银纳米粒子。 透射电子显微镜(TEM)和X射线衍射(XRD)结果显示银纳米粒子的平均粒径为22.7 nm,并具有面心立方晶体结构。 抑菌活性实验结果表明,儿茶素-银纳米复合粒子对大肠杆菌、金黄色葡萄球菌以及白色念球菌都有很强抑制作用,尤其对白色念球菌的抑制作用最强,其最低抑制浓度(MIC)和最低杀菌浓度(MBC)分别为19.63和39.26 μg/mL。 儿茶素-银纳米粒子强抑菌活性可归因于其表面银离子的持续释放,有望应用于长效抑菌制剂产品。     

基于β-环糊精单分散银纳米粒子的绿色合成

以硝酸银为原料,β-环糊精为还原剂和保护剂,一步法合成了粒径为10~30 nm的单分散银纳米粒子,其结构经UV-Vis,FT-IR,XRD和TEM表征。研究了pH、反应温度和γ[n(1)∶n(AgNO_3)]对反应的影响,并提出了银纳米粒子的形成机制。     

立方体形PbS纳米晶的制备

在60～100 ℃下，以醋酸铅为铅源，硫代乙酰胺为硫源，乙二胺为溶剂，制备了立方体形的PbS纳米晶，采用XRD、TEM、SAED、SEM等对合成的产物进行了形貌和结构的表征。结果表明得到的产物为单晶的立方体形PbS，颗粒大小均匀。并且随着反应时间的延长，反应温度的升高，硫源比例的增加，立方体变大。通过控制不同的反应条件，可以合成边长从几十个纳米到几百个纳米的立方体形PbS晶体。     

用双还原法制备三角形银纳米片及其光学性能

在硼氢化钠和柠檬酸三钠共存的体系中还原硝酸银, 以聚乙烯吡咯烷酮(PVP)为表面活性剂和保护剂, 水浴加热制备得到三角形银纳米片, 用X射线衍射(XRD)、透射电子显微镜(TEM)、紫外-可见(UV-Vis)吸收光谱、表面增强拉曼散射(SERS)光谱对其进行了表征. 结果表明: 三角形银纳米片产物为立方相金属银, 边长为(100±40) nm, 厚度为(10±5) nm; 产物表现出与球形银纳米粒子完全不同的吸收光谱; 柠檬酸根在银晶核不同晶面的选择吸附、PVP的包覆作用及Ag(111)晶面的层错对产物的形成起决定作用; 与球形纳米颗粒相比, 三角形银纳米片膜对吡啶(Py)分子有显著的SERS活性.     

银纳米颗粒的绿色可控合成及光催化性能的研究

以桑葚植物提取液为还原剂和稳定剂,合成了单分散的类球形、多晶银纳米颗粒。采用紫外-可见分光光度计、透射电子显微镜和选区电子衍射,对银纳米颗粒的形貌、成分及微观结构进行了表征。在可控合成的基础上,以2-、3-、4-硝基苯酚(2-、3-、4-NP)为目标污染物,考察了银纳米颗粒的光催化性能。结果表明,在太阳光照射下,银纳米颗粒展现出了高的光催化活性和稳定性(90天)。2-、3-、4-NP降解反应的动力学速率常数关系如下:K_(4-NP)K_(2-NP)K_(3-NP)。其中,4-NP降解反应的动力学速率常数最大可达0.33 min~(-1),并可由降解体系中银纳米颗粒的添加量来线性调控。     

原位还原法制备SBA-15介孔分子筛负载纳米银颗粒

利用一种温和的还原剂六亚甲基四胺(HMT)通过一步合成的方法制备了介孔Ag/SBA-15分子筛, 采用粉末X射线衍射(XRD)、透射电镜(TEM)和氮气吸附/脱附等手段对样品进行了表征. 样品的比表面积为525 m²/g, 平均孔径为5.4 nm. 用XPS、广角XRD和高分辨TEM等手段证实样品中的银为金属态的纳米颗粒. 研究结果表明, 以六亚甲基四胺为还原剂通过原位还原的方法能使银纳米颗粒较好地分散到介孔材料的孔道中.     

Green, effective chemical route for the synthesis of silver nanoplates in tannic acid aqueous solution

Silver nanoplates, with average size tunable from 50 to 500 nm, have been synthesized via a simple room-temperature tannic acid (TA) solution-phase chemical reduction method. The synthesis was a seedless process in which tannic acid was used as a reducing as well as a capping agent, and did not need any other surfactant or capping agent to direct the anisotropic growth of the silver nanoparticles. The morphology of silver nanoplates has been confirmed by transmission electron microscopy, the growth process of nanoplates has been studied by UV/vis spectroscopy. Control experiments have been explored for a more thorough understanding of the growth mechanism. It was found that both the concentrations of TA and the pH of solution were the key elements to control the morphology silver nanoplates. The optical in-plane dipole plasmon resonance bands of these silver plates could be tuned from 520 to 1100 nm.     

简单的溶剂热法制备分层的碲化铋微米结构

采用简单的溶剂热法制备出高纯度的由纳米片自组装而形成的碲化铋微米结构。在碲化铋的形成中,乙二醇不仅作为溶剂,而且还作为还原剂。研究发现,聚乙烯吡咯烷酮(PVP)和硝酸在碲化铋的形成中起到了很重要的作用。通过X-射线衍射(XRD)、X-射线光电子能谱(XPS)、扫描电镜(SEM)、透射电镜(TEM)、高分辨透射电镜(HRTEM)、选区电子衍射(SAED)对其进行表征及研究。最后,利用时间演化实验对碲化铋的形成机理进行了探讨。     

阴离子氨基酸表面活性剂调控下水热合成羟基磷灰石纳米片

利用水热合成方法, 在含有氨基酸结构的阴离子表面活性剂N-酰基十二烷基肌氨酸钠(Sar-Na)的控制下, 合成具有较大长径比(aspect ratio)的片状纳米羟基磷灰石晶体. 采用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射(XRD)和傅立叶变换红外(FTIR)光谱表征, 并分析了合成产物的形貌、结构和组成. 结果表明, 在Sar-Na的调控下合成了长度0.5-1.0 μm、宽约30 nm的片状羟基磷灰石晶体, 其长径比约为20:1. 考察了表面活性剂Sar-Na的用量对羟基磷灰石形貌的影响. 随着Sar-Na的添加及用量的增加, 羟基磷灰石由椭圆形变为长片状, 并且片的两端逐渐变尖. 结果显示了Sar-Na对羟基磷灰石形貌的控制作用, 为合成具有较大长径比的羟基磷灰石纳米片提供了一个新的途径.     

银纳米线的制备及电催化还原氧性能研究

分别以聚乙烯基吡咯烷酮(PVP),乙二醇作为软模板和还原剂,采用不同晶种(AgCl、Ag)快速合成了银纳米线.通过SEM和TEM表征,证明合成银纳米线材料形貌均一,颗粒含量很少.并且发现以AgCl为晶种合成的银纳米线长径比为200左右(SNWH),而以Ag为晶种合成的长径比为30左右(SNWL).以银纳米线作为电催化氧...     

A systematic study of the synthesis of silver nanoplates: is citrate a "magic" reagent?

In this work we have carried out systematic studies and identified the critical role of hydrogen peroxide instead of the generally believed citrate in the well-known chemical reduction route to silver nanoplates. This improved understanding allows us to develop consistently reproducible processes for the synthesis of nanoplates with high efficiency and yields. By harnessing the oxidative power of H(2)O(2), various silver sources including silver salts and metallic silver can be directly converted to nanoplates with the assistance of an appropriate capping ligand, thus significantly enhancing the reproducibility of the synthesis. Contrary to the previous conclusion that citrate is the key component, we have determined that the group of ligands with selective adhesion to Ag (111) facets can be expanded to many di- and tricarboxylate compounds whose two nearest carboxylate groups are separated by two or three carbon atoms. We have also found that the widely used secondary ligand polyvinylpyrrolidone can be replaced by many hydroxyl group-containing compounds or even removed entirely while still producing nanoplates of excellent uniformity and stability. In addition to the general understanding of NaBH(4) as a reducing agent, it has also been found to act as a capping agent to stabilize the silver nanoparticles, prolong the initiation time required for nanoplate nucleation, and contribute to the control of the thickness as well as the aspect ratio of silver nanoplates. The improved insight into the specific roles of the reaction components and significantly enhanced reproducibility are expected to help elucidate the formation mechanism of this interesting nanostructure.     

One-step synthesis of large-aspect-ratio single-crystalline gold nanorods by using CTPAB and CTBAB surfactants

Gold nanorods were prepared in high yields by using a one-step seed-mediated process in aqueous cetyltripropylammonium bromide (CTPAB) and cetyltributylammonium bromide (CTBAB) solutions in the presence of silver nitrate. The diameters of the nanorods range from 3 to 11 nm, their lengths are in the range of 15 to 350 nm, and their aspect ratios are in the range of 2 to 70. The diameters of the Au nanorods obtained from one growth batch in CTPAB solutions decrease as their lengths increase, and their volumes decrease as the aspect ratios increase. The diameters of the Au nanorods obtained from one growth batch in CTBAB solutions first decrease and then slightly increase as their lengths increase, and their volumes increase as the aspect ratios increase. These Au nanorods are single-crystalline and are seen to be oriented in either the [100] or [110] direction under transmission electron microscopy imaging, irrespective of their sizes. To the best of our knowledge, this is the first report of the preparation by using wet-chemistry methods of single-crystalline Au nanorods with aspect ratios larger than 15.     

花状铜锌锡硫纳米颗粒的溶剂热法制备和结构表征

以金属氯化物为金属源,硫脲为硫源,聚乙二醇和乙二醇为混合溶剂,采用溶剂热法一步合成了花状的铜锌锡硫纳米颗粒.利用X射线衍射仪,扫描电子显微镜、能谱仪、透射电子显微镜、紫外-可见分光光度计分析了铜锌锡硫纳米颗粒的物相、结构、形貌及光学性能,并初步探讨了铜锌锡硫的生长机理.结果表明,所得到的铜锌锡硫纳米颗粒具有锌黄锡矿结构,直径在500～2 000nm范围内可调,其中花状的铜锌锡硫纳米颗粒由大量厚度约25nm的纳米片构成.所制备的铜锌锡硫纳米颗粒对可见光具有明显的吸收;利用外延法推算得到其禁带宽度约为1.5eV,与太阳能电池所需的最佳禁带宽度相近,显示其有望在新一代太阳能电池中得到应用和推广.     

An effective hydrothermal route for the synthesis of multiple PDDA-protected noble-metal nanostructures

In this article, we demonstrate an effective hydrothermal route for the synthesis of multiple PDDA-protected (PDDA = poly(diallyl dimethylammonium) chloride) noble-metal (including silver, platinum, palladium, and gold) nanostructures in the absence of any seeds and surfactants, in which PDDA, an ordinary and water-soluble polyelectrolyte, acts as both a reducing and a stabilizing agent. Under optimal experimental conditions, Ag nanocubes, Pt and Pd nanopolyhedrons, and Au nanoplates can be obtained, which were characterized by transmission electron microscopy , scanning electron microscopy, energy-dispersive spectroscopy, and X-ray diffraction. More importantly, the nanostructures synthesized show potential applications in surface-enhanced Raman scattering and electrocatalysis, in which Ag nanocubes and Pt nanopolyhedrons were chosen as the examples, respectively.