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．     

Separating Growth from Nucleation for Facile Control over the Size and Shape of Palladium Nanocrystals

In order to maximize the performance of nanocrystals in a specific application, it is necessary to control both their size and shape. Here we report a one-pot protocol that allows us to separate growth from nucleation for achieving better control over the size and shape of Pd nanocrystals. The two processes are temporally separated from each other, although the synthesis is carried out in the same reaction container. Size control is achieved by simply varying the ratio between the amounts of precursor allocated to the growth and nucleation processes. With the involvement of seeds at a fixed number, increasing the amount of precursor for growth leads to increasingly larger nanocrystals. Shape control is made possible by varying the capping agent, with bromide leading to a cubic shape and citrate inducing the formation of an octahedral shape. The synthesis can also be scaled up by at least tenfold without compromising the quality.     

Formation of orientation-ordered superlattices of magnetite magnetic nanocrystals from shape-segregated self-assemblies

Magnetic magnetite (Fe3O4) nanocrystals have been synthesized by combining nonhydrolytic reaction with seed-mediated growth. The shape of these magnetite nanocrystals can be controlled either as pure spheres or a mixture of mainly faceted nanocrystals. Faceted magnetite nanocrystals consist of truncated tetrahedral platelets (TTPs), truncated octahedrons (TOs), and octahedrons (OTs). Transmission electron microscopy analysis indicates that the faceted nanocrystal mixture tends to self-segregate based upon the shape in a self-assembly process, and each shape forms its own distinct crystallographic orientation-ordered superlattice assemblies. Self-assemblies of the Fe3O4 nanocrystals in the shapes of TTP, TO, and OT show hexagonal, primitive cubic, and distorted body-centered cubic (bcc) superlattice structures, respectively. The possible mechanism for the formation of different superstructures is attributed to van der Waals interactions. Nanocrystals with different shapes provide diverse building blocks for bottom-up approaches in building nano- and mesosystems. Furthermore, the self-segregation phenomenon of different shaped nanocrystals in self-assembly processes could be very important in envisioning efficient assembly strategies for nanoscience- and nanotechnology-based devices.     

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.     

Side reactions in controlling the quality, yield, and stability of high quality colloidal nanocrystals

Effects of side reactions during the formation of high quality colloidal nanocrystals were studied using ZnO as a model system. In this case, an irreversible side reaction, formation of esters, was identified to accompany formation of ZnO nanocrystals through the chemical reaction between zinc stearate and an excess amount of alcohols in hydrocarbon solvents at elevated temperatures. This irreversible side reaction made the resulting nanocrystals stable and with nearly unity yield regardless of their size, shape, and size/shape distribution. Ostwald ripening and intraparticle ripening were stopped due to the extremely low solubility/stability of the possible monomers because all free ligands in the solution were consumed by the side reaction. However, focusing on size distribution and 1D growth that are needed for the growth of high quality nanocrystals could still occur for high yield reactions. Upon the addition of a small amount of stearic acid or phosphonic acid, immediate partial dissolution of ZnO nanocrystals took place. Although the excess alcohol could not react with the resulting zinc phosphonic acid salt, it could force the newly formed zinc stearate gradually but completely back onto the existing nanocrystals. The results in this report indicate that side reactions are extremely important for the formation of high quality nanocrystals by affecting their quality, yield, and stability under growth conditions. Due to their lack of information in the literature and obvious practical advantages, studies of side reactions accompanying formation of nanocrystals are important for both fundamental science related to crystallization and industrial production of high quality nanocrystals.     

Shape control and associated magnetic properties of spinel cobalt ferrite nanocrystals

By combining nonhydrolytic reaction with seed-mediated growth, high-quality and monodisperse spinel cobalt ferrite, CoFe(2)O(4), nanocrystals can be synthesized with a highly controllable shape of nearly spherical or almost perfectly cubic. The shape of the nanocrystals can also be reversibly interchanged between spherical and cubic morphology through controlling nanocrystal growth rate. Furthermore, the magnetic studies show that the blocking temperature, saturation, and remanent magnetization of nanocrystals are solely determined by the size regardless the spherical or cubic shape. However, the shape of the nanocrystals is a dominating factor for the coercivity of nanocrystals due to the effect of surface anisotropy. Such magnetic nanocrystals with distinct shapes possess tremendous potentials in fundamental understanding of magnetism and in technological applications of magnetic nanocrystals for high-density information storage.     

一氧化碳辅助钯、铂纳米晶的形貌控制

形貌控制对调控贵金属纳米晶的催化和光学性能至关重要．近年来,在发展铂、钯纳米晶的形貌控制的方法过程中,一氧化碳（CO）不仅作为合成铂、钯纳米晶的优良还原剂,还可通过在特定晶面的选择性吸附辅助铂、钯纳米晶的形貌控制．CO辅助铂、钯纳米晶形貌控制的方法正逐步展现出独特的优越性,甚至帮助我们制备了一些目前其他方法所无法制备的纳米晶．该综述文章首先从表面科学的角度分析讨论CO分子在铂、钯单晶面上的不同吸附行为,然后总结分析了CO调控铂、钯纳米晶形貌的几个典型例子（超薄钯纳米片、介晶钯纳米花、钯四角叉／四面体以及铂纳米立方体、铂钴削角八面体）,讨论了CO在控制铂、钯纳米晶的形貌控制作用及其化学本质,最后提出CO在辅助贵金属纳米晶的形貌控制中的挑战和展望．     

Control of nucleation and growth of gold nanoparticles in AOT/Span80/isooctane mixed reverse micelles

In this study, we demonstrate that mixed reverse micelles are good candidates to be used as nanoreactors for formation of shape-controlled high-quality colloidal nanocrystals and nanowires under mild conditions. Manipulation of the rate of nucleation and subsequent growth of the Au in the mixed reverse micelles induce drastic changes in the particle shape and structure. Here we demonstrate that control of the nucleation and growth kinetics of the Au in the mixed reverse micelles can be used to vary the shapes of the resulting particles from a nearly spherical morphology to cylinders, trigons and cubics. The characterization of the resultant particles, the effects of synthesis conditions (such as concentration of NaCl, addition of glycerol, and reaction temperature) on particle sizes, particle size distribution, and shape of particle formation have been investigated. This study will help us to understand the chemical control synthesis of crystal growth processes at the atomic level.     

Nearly monodisperse and shape-controlled CdSe nanocrystals via alternative routes: nucleation and growth

The nucleation and growth of colloidal CdSe nanocrystals with a variety of elongated shapes were explored in detail. The critical size nuclei for the system were magic sized nanoclusters, which possessed a sharp and dominated absorption peak at 349 nm. The formation of the unique magic sized nuclei in a broad monomer concentration range was not expected by the classic nucleation theory. We propose that this was a result of the extremely high chemical potential environment, that is, very high monomer concentrations in the solution, required for the growth of those elongated nanocrystals. The shape, size, and size/shape distributions of the resulting nanocrystals were all determined by two related factors, the magic sized nuclei and the concentration of the remaining monomers after the initial nucleation stage. Without any size sorting, nearly monodisperse CdSe quantum structures with different shapes were reproducibly synthesized by using the alternative cadmium precursors, cadmium-phosphonic acid complexes. A reasonably large excess of the cadmium precursor, which is less reactive than the Se precursor, was found beneficial for the system to reach the desired balance between nucleation and growth. The shape evolution and growth kinetics of these elongated nanocrystals were consistent with the diffusion-controlled model proposed previously. The branched nanocrystals had to grow at very high monomer concentrations because the multiple growth centers at the end of each branch must be fed with a very high diffusion flux to keep all branches in the 1D-growth mode. The rice-shaped nanocrystals were found as special products of the 3D-growth stage. The growth of the nanocrystals in the 1D-growth stage was proven to be not unidirectional after the length of the nanocrystals reached a certain threshold. Experimental results indicate that coordinating solvents and two ligands with distinguishable coordinating abilities are both not intrinsic requirements for the growth of elongated CdSe nanocrystals.     

Shape evolution of single-crystalline iron oxide nanocrystals

Shape- and size-controlled synthesis of single-crystalline maghemite (gamma-Fe2O3) nanocrystals are performed by utilizing a solution-based one-step thermolysis method. Modulating the growth parameters, such as the type and amount of capping ligands as well as the growth time, is shown to have a significant effect on the overall shape and size of the obtained nanocrystals and on the ripening process itself. The resulting shapes of the novel structures are diverse, including slightly faceted spheres, diamonds, prisms, and hexagons, all of which are in fact truncated dodecahedron structures with different degrees of truncation along the {111}, {110}, or {100} faces. Spherical nanocrystals are easily assembled into the three-dimensional superlattices, demonstrating the uniformity of these nanocrystals. The size-dependent magnetic properties are examined, and large hexagon-shaped gamma-Fe2O3 nanocrystals are shown to be ferrimagnetic at room temperature.     

Pt nanocrystals: shape control and Langmuir-Blodgett monolayer formation

We report the synthesis of monodisperse Pt nanocrystals with three different shapes-cubes, cuboctahedra, and octahedra, selectively, with similar sizes of 9-10 nm by a modified polyol process. We found that addition of silver ion enhances the crystal growth rate along 100, and essentially determines the shape and surface structure of the Pt nanocrystals. After the reaction, the silver species can be easily removed by repetitive precipitation giving pure Pt nanoparticles. Two-dimensional arrays of the Pt nanocrystals were assembled by using the Langmuir-Blodgett (LB) method. The particles were evenly distributed on the entire substrate, and their surface coverage and density can be precisely controlled by tuning the surface pressure. The resulting Pt LB layers are potential candidates for 2-D model catalysts as a result of their high surface area and the structural uniformity of the metal nanocrystals.     

Single-crystalline star-shaped nanocrystals and their evolution: programming the geometry of nano-building blocks

We demonstrate a novel synthetic scheme that can be used to differentially guide the shape of PbS semiconductor nanocrystals. Our study first demonstrates the discovery of single-crystalline star-shaped nanocrystals as novel transient species. We then carefully probe their shape evolution toward other novel nanostructures (e.g., tadpole-, L-, T-, cross-shapes, highly faceted star shapes, truncated octahedrons and cubes, etc.) and systematically elucidate the key parameters that control these final structures. In principle, through programming these growth parameters, the desired architecture of building blocks of other kinds of nano materials can be constructed.     

Seed‐Mediated Growth of Colloidal Metal Nanocrystals

Seed‐mediated growth is a powerful and versatile approach for the synthesis of colloidal metal nanocrystals. The vast allure of this approach mainly stems from the staggering degree of control one can achieve over the size, shape, composition, and structure of nanocrystals. These parameters not only control the properties of nanocrystals but also determine their relevance to, and performance in, various applications. The ingenuity and artistry inherent to seed‐mediated growth offer extensive promise, enhancing a number of existing applications and opening the door to new developments. This Review demonstrates how the diversity of metal nanocrystals can be expanded with endless opportunities by using seeds with well‐defined and controllable internal structures in conjunction with a proper combination of capping agent and reduction kinetics. New capabilities and future directions are also highlighted.     

Low-temperature synthesis of soluble and processable organic-capped anatase TiO2 nanorods

We demonstrate the controlled growth of high aspect ratio anatase TiO2 nanorods by hydrolysis of titanium tetraisopropoxide (TTIP) in oleic acid (OLEA) as surfactant at a temperature as low as 80 degrees C. Chemical modification of TTIP by OLEA is proven to be a rational strategy to tune the reactivity of the precursor toward water. The most influential factors in shape control of the nanoparticles are investigated by simply manipulating their growth kinetics. The presence of tertiary amines or quaternary ammonium hydroxides as catalysts is essential to promote fast crystallization under mild conditions. The novelty of the present approach relies on the large-scale production of organic-capped TiO2 nanocrystals to which standard processing of colloidal nanocrystals, such as surface ligand exchange, can be applied for the first time. Concentrated colloidal titania dispersions can be prepared for a number of fundamental studies in homogeneous solutions and represent a new source of easily processable oxide material for many technological applications.     

水热合成CdS纳米晶体的形貌控制研究

研究了水热合成CdS纳米晶体形貌的化学控制，选择不同的络合试剂为模板,研究其对水热合成CdS纳米晶体形貌的影响.实验发现若以络合试剂乙二胺、甲胺为模板时，产品CdS晶体的形貌分别为（20～30） nm×（200～600） nm和（40～50） nm×（200～600） nm尺寸的纳米棒;而以络合试剂吡啶、 氨为模板时，产品CdS晶体的形貌分别为平均尺寸约30 nm和20 nm的纳米颗粒.用XRD、TEM、XPS、PL和Raman光谱等技术对所得CdS纳米棒进行了表征.同时对水热合成CdS纳米晶体形貌的模板控制机制进行了探讨，提出了一种水热合成CdS纳米棒的络合物结构诱导生长机理.     

Partikel‐Morphologien und Festkörper‐Eigenschaften. Gestalten in der Nanowelt

Nanometer‐sized solids of uniform size distribution and well‐defined morphology often show a clear correspondence between shape and specific physico‐chemical properties that eventually may lead to a particular functionality. This contribution is about the potential of morphologically well‐defined nanocrystals to serve as model systems for the detailed exploration of chemical surface and bulk processes. Moreover, also with respect to synthesis and engineering of functional materials they are of great interest. As basic building block elements they can be utilized for the orientation dependent growth of complex nanostructures.     

Spontaneous transformation of CdTe nanoparticles into angled Te nanocrystals: from particles and rods to checkmarks, X-marks, and other unusual shapes

CdTe nanoparticles spontaneously transform into the branched Te nanocrystals with the unique, highly anisotropic shape of checkmarks after partial removal of the stabilizers of L-cysteine. The Te checkmarks are made in a relatively high yield and uniformity; the length of the arms is ca. 150 nm, whereas the angle between the arms is 74 degrees . Subsequent growth of the particle yields mothlike nanocrystals retaining geometrical anisotropy. Unlike the previous synthesis methods of branched nanocrystals, they are formed via a merger of individual rod-shaped crystallites. High-energy crystal faces on their apexes act as the sticky points causing the particles to join in the ends. This is the first demonstration of spontaneous transformation of binary semiconductor particles into highly anisotropic nanocolloids in an angled conformation. The end reactivity of starting Te rods can be used both for bottom-up fabrication of nanoscale electronics and relatively safe and nontoxic method of synthesis of Te-based optical and other materials.     

Surface Capping Agents and Their Roles in Shape‐Controlled Synthesis of Colloidal Metal Nanocrystals

Surface capping agents have been extensively used to control the evolution of seeds into nanocrystals with diverse but well‐controlled shapes. Here we offer a comprehensive review of these agents, with a focus on the mechanistic understanding of their roles in guiding the shape evolution of metal nanocrystals. We begin with a brief introduction to the early history of capping agents in electroplating and bulk crystal growth, followed by discussion of how they affect the thermodynamics and kinetics involved in a synthesis of metal nanocrystals. We then present representative examples to highlight the various capping agents, including their binding selectivity, molecular‐level interaction with a metal surface, and impacts on the growth of metal nanocrystals. We also showcase progress in leveraging capping agents to generate nanocrystals with complex structures and/or enhance their catalytic properties. Finally, we discuss various strategies for the exchange or removal of capping agents, together with perspectives on future directions.     

球状、立方状及空心立方状PbS纳米晶的控制合成及其形成机理

以醋酸铅为铅源,硫代乙酰胺为硫源,在表面活性剂十二烷基硫酸钠(SDS)和十六烷基三甲基溴化铵(CTAB)共同作用下,通过简单地调节水热反应的反应温度控制合成出球状、立方状和空心立方状PbS纳米晶。利用XRD、TEM对合成产物的结构和形貌进行了表征,发现合成的球状、立方状和空心立方状PbS纳米晶尺寸均一,直径为100 nm左右。对球状、立方状和空心立方状PbS纳米晶的形成机理进行了初探,结果表明反应温度较低时,水热反应初始阶段形成的PbS小颗粒呈球形,在表面活性剂SDS的烷基链模板和CTAB微胶束软模板共同作用下生成球状PbS纳米晶;反应温度较高时,水热反应初始阶段形成的PbS小颗粒由于自身的立方相岩盐晶体结构的影响有呈立方状趋势,在SDS和CTAB共同作用下产物堆积成空心立方体状或立方状。     

Shape evolution of Cu2O nanostructures via kinetic and thermodynamic controlled growth

We report the shape evolution process of Cu(2)O nanocrystals upon slow oxidation of Cu under ambient conditions, yielding novel hexagonal and triangular platelike morphologies. The shape of the obtained nanocrystals evolves from hexagonal to triangular to octahedral; the growth patterns are governed by kinetically and thermodynamically controlled growth. Preferential adsorption of I(-) on {111} planes of Cu(2)O nanoparticles induced the selective crystal growth of metastable platelike structures with {111} faces as the basal planes. On aging, the growth process appeared to shift into the thermodynamic regime and the thermodynamically stable octahedral shape is obtained. The possible growth mechanisms were investigated by varying the synthetic conditions. The band gap of Cu(2)O nanooctahedrons was determined by the classical Tauc approach to be 2.24 eV, which is blue shifted with respect to the bulk Cu(2)O value (2.17 eV). Results suggest that the slow oxidation process and use of crystallographic selective surfactants are essential for the appearance of anisotropic metastable shapes. In general, surface energy control by surfactant molecules might provide a convenient channel for tailoring nanocrystal shapes of metal oxides.