Defect-Directed Growth of Symmetrically Branched Metal Nanocrystals

Branched plasmonic nanocrystals (NCs) have attracted much attention due to electric field enhancements at their tips. Seeded growth provides routes to NCs with defined branching patterns and, in turn, near-field distributions with defined symmetries. Here, a systematic analysis was undertaken in which seeds containing different distributions of planar defects were used to grow branched NCs in order to understand how their distributions direct the branching. Characterization of the products by multimode electron tomography and analysis of the NC morphologies at different overgrowth stages indicate that the branching patterns are directed by the seed defects, with the emergence of branches from the seed faces consistent with minimizing volumetric strain energy at the expense of surface energy. These results contrast with growth of branched NCs from single-crystalline seeds and provide a new platform for the synthesis of symmetrically branched plasmonic NCs.     

Defect‐Directed Growth of Symmetrically Branched Metal Nanocrystals

Branched plasmonic nanocrystals (NCs) have attracted much attention due to electric field enhancements at their tips. Seeded growth provides routes to NCs with defined branching patterns and, in turn, near‐field distributions with defined symmetries. Here, a systematic analysis was undertaken in which seeds containing different distributions of planar defects were used to grow branched NCs in order to understand how their distributions direct the branching. Characterization of the products by multimode electron tomography and analysis of the NC morphologies at different overgrowth stages indicate that the branching patterns are directed by the seed defects, with the emergence of branches from the seed faces consistent with minimizing volumetric strain energy at the expense of surface energy. These results contrast with growth of branched NCs from single‐crystalline seeds and provide a new platform for the synthesis of symmetrically branched plasmonic NCs.     

Architectural control syntheses of CdS and CdSe nanoflowers, branched nanowires, and nanotrees via a solvothermal approach in a mixed solution and their photocatalytic property

Wurtzite CdS and CdSe nanostructures with complex morphologies such as urchin-like CdS nanoflowers, branched nanowires, and fractal nanotrees can be produced via a facile solvothermal approach in a mixed solution made of diethylenetriamine (DETA) and deionized water (DIW). The morphologies of CdS and CdSe nanocrystals can be easily controlled via tuning the volume ratio of DETA and DIW. Urchin-like CdS nanoflowers made of CdS nanorods are in a form of highly ordered hierarchical structures, while the nanowires are branched nanowires, and the fractal CdS nanotrees are a buildup of branched nanopines. The results demonstrated that solvothermal reaction in a mixed amine/water can access a variety of complex morphologies of semiconductor materials. The photocatalytic activity of CdS particles with different morphologies has been tested by the degradation of acid fuchsine under both UV and visible light, showing that the as-prepared branched CdS nanowires exhibit high photocatalytic activity for degradation of acid fuchsine.     

In situ hydrophobized, shape-anisotropic nanoparticles for composite materials

An inverse emulsion technique which allows the anisotropic growth of a broad variety of inorganic nanoparticles, together with an efficient hydrophobization, is described. This method is based upon the combined use of amphiphilic copolymers, which act as emulsifiers as well as compatibilizers, and structure-directing agents that control the crystallization of the inorganic nanoparticles. As a consequence, water-soluble, structure-directing agents can now be applied for the synthesis of hydrophobic, shape-anisotropic nanocrystals. More precisely, spherical, rod-like, and branched CdS as well as Au nanoparticles were prepared. Due to their excellent hydrophobization, these particles were homogeneously incorporated into a poly(2-ethylhexyl methacrylate) matrix. Their shape-dependent properties were transferred to nanocomposites as demonstrated for branched CdS nanocrystals. In comparison to more traditional materials composed of branched CdS nanoparticles, which are stabilized by low molecular weight amphiphiles, our composites show much less scattering. This is due to the homogenous distribution of the nanoparticles in the matrix.     

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．     

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.     

Branching phenomena in nanostructure synthesis illuminated by the study of Ni-based nanocomposites

Branching phenomena are ubiquitous in both natural and artificial crystallization processes. The branched nanostructures'' emergent properties depend upon their structures, but their structural tunability is limited by an inadequate understanding of their formation mechanisms. Here we developed an ensemble of Nickel-Based nano-Composites (NBCs) to investigate branching phenomena in solution-phase synthesis with precision and in depth. NBCs of 24 morphologies, including dots, core@shell dots, hollow shells, clusters, polyhedra, platelets, dendrites, urchins, and dandelions, were synthesized through systematic adjustment of multiple synthesis parameters. Relationships between the synthesis parameters and the resultant morphologies were analyzed. Classical or non-classical models of nucleation, nascent growth, 1D growth, 2D growth, 3D reconstruction, aggregation, and carburization were defined individually and then integrated to provide a holistic view of the formation mechanism of branched NBCs. Finally, guidelines were extracted and verified to guide the rational solution-phase syntheses of branched nanomaterials with emergent biological, chemical, and physical properties for potential applications in immunology, catalysis, energy storage, and optics. Demonstrating a systematic approach for deconvoluting the formation mechanism and enhancing the synthesis tunability, this work is intended to benefit the conception, development, and improvement of analogous artificial branched nanostructures. Moreover, the progress on this front of synthesis science would, hopefully, deepen our understanding of branching phenomena in nature.

Here we developed an ensemble of Nickel-Based nano-Composites (NBCs) to investigate the branching phenomena in solution-phase synthesis with precision and in depth.     

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.     

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.     

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.     

Direct synthesis of branched gold nanocrystals and their transformation into spherical nanoparticles

We report a facile synthesis of branched gold nanocrystals by the addition of a suitable amount of NaOH to an aqueous solution of cetyltrimethylammonium bromide (CTAB), HAuCl(4), and ascorbic acid. The branched nanocrystals were formed within minutes of reaction and showed monopod, bipod, tripod, and tetrapod structures. They are crystalline and have smooth surfaces. These gold multipods are kinetically controlled products and are thermodynamically unstable. The branched nanocrystals quickly transformed into spherical nanoparticles within 1 h of reaction, and the process was essentially complete after 2 days. The morphological transformation has been monitored by both UV-vis absorption spectroscopy and electron microscopy. The appearance of two major absorption bands for the branched gold nanocrystals eventually became only a single band at 529 nm for the spherical nanoparticles. The resulting nanoparticles are single crystals with diameters of 20-50 nm and do not show a faceted structure. When the freshly prepared branched nanocrystals are kept in a refrigerator at 4 degrees C, their multipod structure can be preserved for over a month without significant spectral shifts.     

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.     

Heterostructured Tin oxide-pillared tetratitanate with enhanced photocatalytic activity

Here we point out that the nanocrystals well ordered in compact hexagonal networks are highly stable compared to the same nanocrystals either isolated on a substrate or ordered in a less compact manner. The emergence of unexpected collective physical intrinsic properties results in the nanocrystals being ordered over a long distance in colloidal crystals called supracrystals. Some morphologies of nanocrystals ordered, at the micrometer scale, in 3D superlattices called supracrystals are similar to those obtained with atoms in nanocrystals. From a comparison between vibrational and magnetic properties of supracrystals and aggregates composed of the same nanocrystals, it is proposed that nanocrystals in a supracrystal could behave as atoms in a nanocrystal. From these data a possible analogy between nanocrystals in a supracrystal and atoms in nanocrystals is proposed.     

Pd纳米晶的调控合成及其在燃料电池中的应用

贵金属Pd纳米晶体的催化性能与其表面结构有着密切联系。基于目前Pd多面体纳米晶体可控合成技术的发展,Pd纳米晶体催化性能的进一步优化及其在催化领域的应用前景依然广阔。本文主要阐述了关于Pd多面体纳米晶的制备及其作为电催化剂在燃料电池中应用的最新研究进展。在介绍纳米晶体的生长机理及其表面结构与晶体形状的关系之后,重点描述了Pd多面体纳米晶体常见的几种制备方法,概述了Pd多面体纳米晶体作为催化剂在燃料电池阴极和阳极中的应用。最后总结展望了Pd多面体纳米晶体作为催化剂的研究方向及其发展前景。     

Controlled Synthesis of Thorium and Uranium Oxide Nanocrystals

Very little is known about the size and shape effects on the properties of actinide compounds. As a consequence, the controlled synthesis of well‐defined actinide‐based nanocrystals constitutes a fundamental step before studying their corresponding properties. In this paper, we report on the non‐aqueous surfactant‐assisted synthesis of thorium and uranium oxide nanocrystals. The final characteristics of thorium and uranium oxide nanocrystals can be easily tuned by controlling a few experimental parameters such as the nature of the actinide precursor and the composition of the organic system (e.g., the chemical nature of the surfactants and their relative concentrations). Additionally, the influence of these parameters on the outcome of the synthesis is highly dependent on the nature of the actinide element (thorium versus uranium). By using optimised experimental conditions, monodisperse isotropic uranium oxide nanocrystals with different sizes (4.5 and 10.7 nm) as well as branched nanocrystals (overall size ca. 5 nm), nanodots (ca. 4 nm) and nanorods (with ultra‐small diameters of 1 nm) of thorium oxide were synthesised.     

Fast Synthesis of PbS Nanocrystals in Aqueous Solution with Shape Evolution from Cubic to Octahedral Structures and Their Assembled Structures

In this study, we have developed for the first time a fast and energy‐efficient method for the synthesis of PbS nanocrystals with systematic shape evolution from cubic to truncated cubic, cuboctahedral, truncated octahedral, and octahedral structures. The method involves the addition of a small volume of preheated lead acetate and thioacetamide (TAA) mixture to an aqueous growth solution of lead acetate, thioacetamide, cetyltrimethylammonium bromide, and nitric acid. By varying the amount of thioacetamide added to the growth solution, PbS nanocrystals with different morphologies were generated in 2 h at 90 °C. Slight experimental modifications were adopted to generate truncated octahedra. The nanocrystals have very uniform dimensions with average sizes of 32–47 nm. Their structures have been extensively examined by electron microscopy. Nanocube sizes can also be tuned within a range. UV/Vis absorption spectra of PbS cubes, cuboctahedra, and octahedra all show decreasing but continuous absorption from 300 nm to beyond 1000 nm. By monitoring the speed of darkening of solution color, particle growth rate was found to be fastest for nanocubes, followed by truncated cubes, cuboctahedra, and octahedra. These monodisperse nanocrystals can readily form self‐assembled structures. Truncated cubes and octahedra that form monolayer and multilayer packing arrangements have also been studied. This green approach to the synthesis of PbS nanocrystals with fine size and shape control should allow for investigations of their facet‐dependent properties and the fabrication of novel heterostructures.     

Synthesis of Zinc Blende CdTe Nanocrystals and Facile Shape Conversion from Multipods to Dot-shaped Particles

Branched CdTe nanocrystals with zinc blende structure were directly synthesized in the early growth stage at a high initial concentration of cadmium precursor and a high molar ratio of Cd precursor to Te precuesor. Activation of the cadmium precursor by octadecylamine was found to be critical for the formation of branched CdTe nanocrystals. Furthermore, these as-prepared CdTe nanocrystals can evolve into nearly monodisperse dots through Ostwald ripening and still keep strong photoluminescence. These results manifest a new route to synthesize branch- and dot-shaped CdTe nanocrystals with zinc blende structure.     

Hyperbranched anatase TiO2 nanocrystals: nonaqueous synthesis, growth mechanism, and exploitation in dye-sensitized solar cells

A colloidal crystal-splitting growth regime has been accessed, in which TiO(2) nanocrystals, selectively trapped in the metastable anatase phase, can evolve to anisotropic shapes with tunable hyperbranched topologies over a broad size interval. The synthetic strategy relies on a nonaqueous sol-gel route involving programmed activation of aminolysis and pyrolysis of titanium carboxylate complexes in hot surfactant media via a simple multi-injection reactant delivery technique. Detailed investigations indicate that the branched objects initially formed upon the aminolysis reaction possess a strained monocrystalline skeleton, while their corresponding larger derivatives grown in the subsequent pyrolysis stage accommodate additional arms crystallographically decoupled from the lattice underneath. The complex evolution of the nanoarchitectures is rationalized within the frame of complementary mechanistic arguments. Thermodynamic pathways, determined by the shape-directing effect of the anatase structure and free-energy changes accompanying branching and anisotropic development, are considered to interplay with kinetic processes, related to diffusion-limited, spatially inhomogeneous monomer fluxes, lattice symmetry breaking at transient Ti(5)O(5) domains, and surfactant-induced stabilization. Finally, as a proof of functionality, the fabrication of dye-sensitized solar cells based on thin-film photoelectrodes that incorporate networked branched nanocrystals with intact crystal structure and geometric features is demonstrated. An energy conversion efficiency of 6.2% has been achieved with standard device configuration, which significantly overcomes the best performance ever approached with previously documented prototypes of split TiO(2) nanostructures. Analysis of the relevant photovoltaic parameters reveals that the utilized branched building blocks indeed offer light-harvesting and charge-collecting properties that can overwhelm detrimental electron losses due to recombination and trapping events.     

Mg2 FeH6 纳米晶的制备及储氢性能

在室温和氩气气氛下, 以MgH2 和纳米Fe为原料, 采用机械合金化(球磨法)制备了Mg2FeH6纳米晶. 考察了球磨参数(时间、 转速)对产物的影响, 对所制备的Mg2FeH6 纳米晶的组成、 结构和形貌进行了表征, 并对其储氢性能进行了测试. 结果表明, 所制备的Mg2FeH6纳米晶为立方结构, 纯度较高(91.4%), 其晶粒尺寸较小, 约为10~30 nm, 但团聚现象较为严重. Mg2FeH6纳米晶具有较低的活化能和较好的吸放氢动力学性能, 其放氢的脱附焓和脱附熵分别为(-42.8±2) kJ/mol和(-72.0±3) J/(mol·K). 在503 K和6 kPa的氢气压力下, Mg2FeH6纳米晶在70 min内放氢量达到2.5%(质量分数); 在2 MPa的氢气压力下, 上述放氢产物具有较快的起始吸氢速率.     

Synthesis of single-crystal beta-Ni(OH)2 nanodisks and alpha-Fe2O3 nanocrystals in C2H5OH-NaOH-NH3 x H2O system

Circular beta-Ni(OH)2 nanodisks and rhombohedral and hexagonal alpha-Fe2O3 nanocrystals were prepared using the C2H5OH-NaOH-NH3 x H2O system under hydrothermal conditions. The C2H5OH/H2O solvent is an appropriate one for the growth of these two materials with their thermodynamically favored morphologies. The possible formation mechanisms are discussed.