纳米粒子的精准组装

纳米材料由于其独特的光、电、磁、力学等性质,成为了构建功能材料与器件的理想基元。实现纳米粒子的精确组装,是探究粒子之间的耦合聚集性质和制备宏观功能器件的基础。但是由于纳米粒子的小尺寸以及在溶液中运动的随机性与复杂性,精准控制纳米粒子组装体的形貌以及在空间中的相对位置仍存在巨大挑战。为了将纳米粒子组装成理想的有序结构,许多控制粒子组装的策略与方法得到发展。本文首先概述了纳米粒子自组装的控制方法与典型形貌,着重分析了影响粒子精准排布的因素与控制方法,并对纳米粒子及其组装体的光学性质与器件应用的最新研究进展进行了讨论,最后对目前纳米粒子精准组装所面临的挑战以及未来发展的方向进行了展望。     

大孔道介孔氧化硅/碳基纳米材料的设计合成与应用

由于具有较大的孔道尺寸、 丰富的化学组成以及广阔的应用前景, 大孔道介孔纳米材料近年来引起了科研工作者的广泛关注. 分别利用复合胶束和无机纳米晶作为结构基元进行可控自组装的软模板法和硬模板法是合成这类大孔道介孔纳米材料最有效的两类方法. 本文总结了一系列基于不同类型软模板或硬模板共组装形成大孔道介孔纳米材料的合成方法和策略, 并讨论了所获得的大孔道介孔纳米材料在催化、 能量转换与存储以及生物医学中的应用. 最后, 对利用新型嵌段聚合物或复杂结构纳米晶合成大孔道介孔纳米材料的前景和挑战进行了展望.     

纳米晶取向接合生长动力学研究及其在量子点发光性质调控中的应用

对晶体生长机制、动力学与微结构衍化的认识是实现纳米材料的尺寸和形貌可控制备的基础．以表面溶解沉积为特征的奥斯特瓦尔德熟化（0R）理论常用来解释传统的晶体生长过程．在该生长模式下,纳米晶体的生长呈现出小颗粒溶解而大颗粒逐渐长大的特征．在纳米材料体系,近来还发现了一种重要的新的晶体生长模式——“取向接合（OA）”机制,在该机制下,两个晶格取向一致的初级纳米颗粒可通过直接接合和结构调整,从而长成一个新的晶体．这一机制已被证实在许多纳米材料体系中广泛存在,并对所合成的纳米材料的形貌、微结构具有非常显著的影响,在构筑新型纳米结构方面具有潜在的优势．本文我们首先回顾了OA生长机制的认识历程和这一机制对材料科学的重大意义;进而,基于我们的研究工作系统介绍了OA生长动力学模型的建立与发展,进一步阐述了这一机制的微观过程及其对材料内部缺陷的特殊影响,深入地分析和讨论了表面包裹的强弱、表面作用的性质对OR机制和OA机制的抑制和调控作用;基于上述表面包裹可调控纳米材料的生长机制的认识,我们结合近期研究结果,从动力学角度分析了量子点的生长机制与其发光特性的内在关联,阐明了表面包裹调控量子点的发光性质的本质原因,为制备不同发光特征的量子点及理解其发光性质衍化规律提供了重要的理论指引．     

功能纳米材料的化学控制合成、组装、结构与性能

维度限制使得纳米材料具有独特的物理和化学性质,如何对纳米构造单元的结构进行调控,并最终将纳米效应在宏观尺度上体现是当今纳米科技面临的挑战性问题,纳米材料的化学控制合成方法学、组装、结构与性能的研究是解决上述问题的基础．这篇综述文章从四个方面,分别介绍了单分散纳米晶以及纳米管、纳米线、空心纳米微球等系列低维纳米结构在合成方法与技术、“自下而上”的组装、基于微结构的性能表征与应用探索等领域取得的研究进展,试图总结出其中的规律性,同时也展现了纳米科学与技术的魅力和广阔的发展前景．     

电荷驱动水中氧化物纳米颗粒自组装的原位透射电子显微镜研究

<正>由于氧化物纳米材料具有较大的比表面积和表面活性,因此被广泛地应用于催化、能源储存、纳米器件等各种领域。人们通过各种不同的合成技术手段,实现对氧化物纳米材料表面形貌进行调控,进而获得具有优异性能的纳米材料。在各种纳米材料合成手段中,可控性自组装技术是一种有效调控纳米材料尺寸及形貌特征的方法,在纳米材料的合成以及制备方面具有较大的应用潜力1。纳米颗粒的自组装过程及其自组装的结构形态特征,常常受到纳米颗粒之间的范德华力、氢键、静电力、疏水性、偶极矩等相互作用的影响2–5。     

形貌可控贵金属纳米颗粒的合成、光学性质及生长机制

近二十年来, 贵金属纳米颗粒由于其独特的性质, 已成为人们广泛研究的课题. 研究人员应用多种方法来合成纳米尺度的贵金属材料并且探讨了纳米材料的性质与尺寸和形状的关系. 本文简单回顾贵金属纳米颗粒的合成方法, 主要讨论纳米颗粒的形状对其光学性质的影响和颗粒的生长机制, 最后简述贵金属纳米材料的应用前景.     

无机纳米晶的形貌调控及生长机理研究

形貌及尺寸规整可控的纳米晶体的合成是目前十分引人注目的纳米材料研究领域．制备合成中的形貌调控及其功能化是这些纳米材料能够得到应用的关键问题．研究者们希望在纳米晶的任一阶段均能实现控制并在期望的阶段停止,从而得到尺寸、形态、结构及组成确定的纳米晶体．本文综述了近年来无机纳米晶体的典型合成路径,深入探讨了纳米晶在成核、生长及熟化阶段的控制原理,研究了液相合成纳米材料过程中晶体结构与生长行为的相关性问题,并总结了几类具有代表性的低维、多维纳米晶体的形成规律和生长机理．探索纳米粒子的调控合成对于纳米材料的规模化生产及应用具有重要的理论价值和指导意义．     

手性模板合成CdS纳米棒

由于纳米材料具有量子尺寸效应及大的比表面积等性质而使其在电子学[1]、光学[2]、催化[3]和陶瓷[4]等领域显示出诱人的应用前景. 近年来纳米材料的制备及纳米技术发展迅速, 特别是具有特殊光电活性的新型无机纳米材料的制备已引起人们的普遍关注. 现在合成纳米材料的方法主要包括反相胶束法[5]、 LB膜法[6]、嵌段共聚物法[7]和模板合成法[8]. 其中模板合成技术不仅可以通过设计新型的模板分子, 还可通过模板分子的不同自组装行为来调控纳米材料的尺寸和形貌. Stupp等[9]曾利用溶致液晶的六方中间相作为模板, 在其纳米孔隙中成功地合成了具有六方排列超晶格纳米结构的材料. 本文以双亲性丙氨酸衍生物为模板, 在不同的化学微环境下合成了结构不同的CdS纳米棒.     

纳米材料的自组装研究进展

本文主要评述了近年来纳米材料自组装的研究进展，即对以纳米材料(包括零维的纳米粒子和一维的纳米管/线)为单元而开展的自组装方面的工作进行了介绍。将纳米材料自组装为各种尺度的有序结构会产生更优异的整体的协同性质，这对于以纳米材料为基础而构筑的微纳米器件有着重要的意义。由于目前纳米材料的研究主要集中在零维和一维体系，因此，本文分别就此两种体系的自组装行为进行了评述。具体内容包括：单分子层薄膜修饰的无机纳米粒子的自组装、大分子修饰的无机纳米粒子的自组装、未被修饰的无机纳米粒子的自组装；表面张力及毛细管力诱导的一维纳米材料的自组装、模板诱导的一维纳米材料的自组装、静电力诱导的一维纳米材料的自组装。     

聚合物控制CuO纳米盘的液相生长

表面活性剂聚丙烯酰胺（PAM）的控制下,在温和的低温水溶液中,高产率的CuO纳米盘被合成。粉未衍射（XRD）,扫描电镜（SEM）,高分辨透射电子显微（HRTEM）对产物的形貌结构进行表征。研究了不同反应条件如温度、PAM浓度等对产物形貌与尺寸的影响。结果表明,CuO纳米盘为单晶结构,沿着（002）和（110）面生长。PAM对纳米盘的形成起到关键作用。典型的聚合物-晶体作用生长机理用来解释CuO纳米盘的形成。聚合物诱引晶体生长与调控纳米晶自组装将提供了一条有效的路径来合成具有复杂形貌与特殊结构的无机和无机-有机杂化材料。     

纳晶的制备及其光谱的尺寸依赖性

用再沉淀法制备了纳米晶体,向体系中加入水溶性高分子聚乙烯醇（PVA）可有效地抑制纳晶的生长,从而制得了稳定的具有不同粒径的纳晶.光谱研究表明,随着纳晶粒径增加,由于纳晶中分子间相互作用的变化,其吸收峰和激发峰位置都发生了红移,同时纳晶中激基缔合物的荧光发射峰强度减弱,荧光寿命有所延长.     

Redox reaction induced Ostwald ripening for size- and shape-focusing of palladium nanocrystals

We report here that size- and shape-focusing can be achieved through the well-known Ostwald ripening process to produce high-quality metal nanocrystals (NCs). Using Pd as an example, we show that the addition of small NCs of appropriate sizes could help in modulating the growth of larger NCs and enable excellent control over both the size and shape uniformity of the products. A detailed mechanistic study showed that the self-focusing of Pd NCs relied on a dissolution and regrowth process induced by redox reaction of HCHO. With the assistance of HCHO, injection of small sacrificial nanocrystals (SNCs), with sizes below a critical value, into larger seeds results in the dissolution of the SNCs and subsequent deposition onto the larger ones, thus allowing the formation of monodisperse Pd NCs. We have identified the critical radius of the SNCs to be ∼5.7 nm for Pd, and verified that SNCs with sizes larger than that could not effectively support the growth of larger seeds. More interestingly, since Ostwald ripening involves matter relocation, this synthetic approach could even break the self-termination growth habits of metal NCs and produce nanocrystals with sizes that are not conveniently accessible by direct growth.     

尿液中的纳米微晶及其与尿石形成的关系

尿石症是一种世界范围的常见病和多发病,其主要的矿物成分为草酸钙(CaOxa)等[1-2]。但至今为止,尿石症形成过程中的许多化学及物理问题尚不清楚:尿液中的微晶是怎样生长和聚集?随后又是怎样黏附到尿路细胞膜上而形成结石?正常人与尿石患者尿液中微晶的数量和尺寸等存在什么样的     

单源前体合成水溶性的CdS和ZnS纳米晶

0引言量子点(QuantumDots)一般指半径小于或接近玻尔激子半径的半导体纳米晶颗粒。和有机染料分子相比,无机半导体纳米晶的带隙宽度可通过简单     

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.     

Effect of Temperature on the Nucleation and Growth of Precious Metal Nanocrystals

Understanding the effect of physical parameters (e.g., temperature) on crystallisation dynamics is of paramount importance for the synthesis of nanocrystals of well‐defined sizes and geometries. However, imaging nucleation and growth is an experimental challenge owing to the resolution required and the kinetics involved. Here, by using an aberration‐corrected transmission electron microscope, we report the fabrication of precious metal nanocrystals from nuclei and the identification of the dynamics of their nucleation at three different temperatures (20, 50, and 100 °C). A fast, and apparently linear, acceleration of the growth rate is observed against increasing temperature (78.8, 117.7, and 176.5 pm min^?1, respectively). This work appears to be the first direct observation of the effect of temperature on the nucleation and growth of metal nanocrystals.     

Synthesis and assembly of monodisperse spherical Cu2S nanocrystals

High-quality monodisperse Cu₂S nanocrystals (sizes from 2 nm to 20 nm) have been successfully synthesized by the reaction of copper stearate (CuSt₂) and dodecanethiol (DDT) in 1-octadecene (ODE). The nanocrystals were characterized using X-ray diffraction (XRD), X-ray photoelectron spectrum (XPS), and transmission electron microscopy (TEM). These as-prepared Cu₂S nanocrystals with certain sizes have been found with good self-assembly behaviors, and they were easily to assemble into two-dimensional and three-dimensional superlattice structures. DDT served as both sulfur source and capping ligand, and was found a key factor to affect the growth and the self-assembly behaviors of the Cu₂S nanocrystals.     

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.     

基于单分散氟化物纳米晶的成核生长模型

在纳米介观尺度范围内实现对材料尺寸与形貌的调控,是纳米材料合成、制备、功能化及其应用的关键,对认识并解纳米晶的成核与生长规律具有重要意义.基于单分散氟化物纳米晶合成提出的扩散控制动力学模型(DCK,diffusion-controlled kinetic)和表面化学热力学模型(SCT,surface chemical thermodynamics)旨在探讨纳米晶的成核与生长规律.本文围绕纳米晶的成核、生长机理,在综述前人工作的基础上,归纳和总结了上述模型,有望对纳米晶的可控合成提供理论指导与借鉴.     

Shape-controlled platinum nanocubes and their assembly into two-dimensional and three-dimensional superlattices

Liquid-liquid phase transfer has been used to synthesize platinum nanocrystals with a cubic morphology. By finely tuning the parameters controlling the nucleation and growth processes, nanometric truncated cubes or perfect cubes may be obtained. To our knowledge, this is the first time such shapes are obtained with this procedure. The importance of both the length of the capping agent to control the growth process and the bromide anions as poison for the (111) facet is shown. The low degree of size polydispersity allows these nanocrystals to self-assemble with a long-range ordering in two-dimensional and three-dimensional supracrystals. According to the nanocrystal shape, simple cubic or face-centered cubic supracrystals are observed. It is remarkable to notice that well-faceted supracrystals with sizes on the order of 10 microm may be obtained.