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 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.     

Self-assembled CuO nanoarchitectures and their catalytic activity in the thermal decomposition of ammonium perchlorate

CuO shuttle-like and flower-like nanocrystals were synthesized through a one-step, low-temperature solution-phase method in the presence of a cation surfactant, hexadecyl trimethyl ammonium bromide. These nanocrystals were studied as an additive for promoting the thermal decomposition of ammonium perchlorate (AP). With the addition of CuO shuttle-like and flower-like nanocrystals, the thermal decomposition temperature of AP decreased. The structure, particle size, and morphology of resulting CuO powders were characterized by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. Thermogravimetric analysis technique was applied to investigate the thermal decomposition of mixtures of AP and as-prepared CuO nanocrystals.     

Selective Synthesis of 2D Mesoporous CuO Agglomerates by Pulsed Spark Discharge in Water

Metal oxide nanomaterials, including copper oxide, have attracted great attention due to their unique physical and chemical properties that are dependent on particle size and morphology. In this study, we propose an alternative technique for the synthesis of 2D mesoporous CuO agglomerates that is both efficient and ecological. This technique is based on the use of pulsed spark discharges between copper electrodes immersed in deionized water. Detailed TEM analyses show that the synthesized CuO nanostructures are composed of elementary nanocrystals with sizes in the order of a few nanometers. Assessments of the effects of applied voltage (5 and 20 kV) and discharge pulse width (100 and 500 ns) demonstrate that the latter parameter influences the size and density of nanocrystals in a nanostructure. Moreover, voltage and pulse width may both be used to finely control the direct optical band gap energy of CuO nanostructures between 3.0 and 3.4 eV. The efficient and ecological technique developed in this study produces 2D mesoporous CuO agglomerates that can be readily used in other processes.

     

Synthesis of Highly Monodisperse Cu2O Nanocrystals and Their Applications as Hole-Transporting Layers in Solution-Processed Light-Emitting Diodes

The synthesis of phase-pure, narrow-size-distributed and highly stable Cu₂O nanocrystals is reported, which can be processed as hole-transporting layers (HTLs) in solution-processed optoelectronic devices. The synthesis is based on a thermal decomposition process with a ligand protection strategy. The reactivity of precursor can be tuned by simply modulating the concentration of oleylamine in non-coordinated solvent, resulting in effectively controlling the size and size distribution of Cu₂O nanocrystals. Combined with ligand protection strategy of using lithium stearate and moderate reaction temperature of 170 °C, in situ aggregation of Cu₂O nanocrystals could be inhibited, exhibiting excellent stability in hexane for several months. The resulting phase-pure colloidal Cu₂O particles (after ozone-treatment) were applied as HTLs in polymer light-emitting diodes, the performance of which are comparable to that of the poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) based devices.     

Cu nanoparticles of low polydispersity synthesized by a double-template method and their stability

Cu nanoparticles of well-defined size and stability were synthesized with the aid of a double-template method. The templates consisted of sodium dodecyl sulfate (SDS) aggregates combined with and wrapped by poly(vinylpyrrolidone) (PVP) chains. Copper sulfate was reduced within the templates resulting in multicrystalline Cu nanoparticles. The size of the particles was uniform. They were capped by PVP–SDS complexes and the shape turned out to be non-spherical. PVP used in the experiments has an average molecular weight of 40,000. In this case, the particle dimensions were essentially determined by the chosen concentration of SDS in the reaction solution. No oxidation of the as-grown copper particles was detected even in the absence of inert gas protection during the synthesis process. When exposed to air at room temperature, Cu nanoparticles capped by PVP–SDS complexes showed much better resistance to oxidation than those without the capping agents. Furthermore, the steric and screening effect of the capping agents permitted the preparation of uniform colloidal dispersions stable over months. The material obtained by this double-template method was found to be very sensitive to the synthesis temperature. At synthesis temperatures above 40 °C, CuO instead of Cu was obtained.     

Synthesis of Pd particles with various shapes by ionic liquids for HFP hydrogenation catalyst

Palladium particles were simply synthesized using various ionic liquids. The morphology of the particles was significantly affected by the anion parts of the ionic liquids. Among the ionic liquids, hexafluorophosphate as an anion part was more effective in forming the palladium particles with relatively small and narrow size distribution. However, irregularly shaped palladium particles were synthesized without ionic liquid assistance. For a hexafluoropropylene hydrogenation to produce hydrofluorocarbons, palladium was impregnated on a carbon powder as a catalyst. During the preparation of the catalyst, ionic liquids were added to control the shape of the palladium on the support. After calcinations at 500 °C, all catalysts possessed the comparable crystal structure. Under identical reaction conditions, the catalyst prepared using 1-hexyl-3-methylimidazolium hexafluorophosphate was the most effective in this reaction. Hence, catalytic activity was mainly determined by the size of the palladium particles.     

Synthesis and size control of monodisperse copper nanoparticles by polyol method

We describe herein the synthesis of metallic copper nanoparticles in the presence of poly(vinylpyrrolidone), employed as a protecting agent, via a polyol method in ambient atmosphere. The obtained copper particles were confirmed by XRD to be crystalline copper with a face-centered cubic (fcc) structure. We observed monodisperse spherical copper nanoparticles with a diameter range 45+/-8 nm. The particle size and its distribution are controlled by varying the synthesis parameters such as the reducing agent concentration, reaction temperature, and precursor injection rate. The precursor injection rate plays an important role in controlling the size of the copper nanoparticles. On the basis of XPS and HRTEM results, we demonstrate that the surface of the copper is surrounded by amorphous CuO and that poly(vinylpyrrolidone) is chemisorbed on the copper surface.     

Nickel sulfide and copper sulfide nanocrystal synthesis and polymorphism

Nickel sulfide and copper sulfide nanocrystals were synthesized by adding elemental sulfur to either dichlorobenzene-solvated (copper sulfide) or oleylamine-solvated metal(II) precursors (nickel sulfide) at relatively high temperature to produce the metal sulfide. Nickel sulfide nanocrystals are cubic Ni(3)S(4) (polydymite) with irregular prismatic shapes, forming by a two-step reduction-sulfidation mechanism where Ni(II) reduces to Ni metal before sulfidation to Ni(3)S(4). Despite extensive efforts to optimize the Ni(3)S(4) nanocrystal size and shape distributions, polydisperse nanocrystals are produced. In contrast, copper sulfide nanocrystals can be obtained with narrow size and shape distributions. The copper sulfide stoichiometry depended on the Cu:S mole ratio used in the reaction: Cu:S mole ratios of 1:2 and 2:1 gave CuS (covellite) and Cu(1.8)S (digenite), respectively. CuS nanocrystals formed as hexagonal disks that assemble into stacked ribbons when cast from solution onto a substrate. CuS, Cu(1.8)S, and Ni(3)S(4) differ from the Cu(2)S and NiS nanocrystals obtained by solventless decomposition of metal thiolate single source precursors, in terms of stoichiometry for copper sulfide, and both stoichiometry and morphology for nickel sulfide [Ghezelbash, A.; Sigman, M. B., Jr.; Korgel, B. A. Nano Lett. 2004, 4, 537-542. Sigman, M. B. Ghezelbash, A.; Hanrath, T.; Saunders, A. E.; Lee, F.; Korgel, B. A. J. Am. Chem. Soc. 2003, 125, 16050-16057].     

Solvothermal syntheses of nano- and micro-sized ZnO powders with a controllable morphology

Zinc oxide powders with different morphologies and grain sizes were synthesized using solvothermal methods from ethanolic zinc acetate solutions in the presence of lithium hydroxide. The influence of the temperature and the time of the reaction, as well as the pH value of the starting solution, on the ZnO particle size and morphology were examined. It was found that an increase in the pH value from 8 to 12 results in a significant decrease in the mean particle size. Also, the particles?? morphology can be changed from hexagonal plates and prisms to rods by controlling the reaction time and the temperature. The crystallization mechanism is discussed, based on established correlations such as the particle size/shape versus the reaction parameters. Dissolution/recrystallisation is the most probable growth mechanism responsible for the ZnO particles?? morphology obtained in the solvothermal (hydrothermal) reactions with a basic solution. The planar structure of the zinc-hydroxy-acetate molecule plays the main role in growing the structures during the sovothermal reactions with a slightly acid solution.     

微乳液合成胶体CuO/γ-Al2O3及其催化芳香硝基化合物还原（英文）

Monodispersed colloidal copper oxide nanoparticles were synthesized by water-in-oil microemulsion using CuCl 2·H2O and NaOH.The effect on CuO particle size was studied by varying the water-to-surfactant molar ratio,precursor concentration and molar ratio of NaOH to CuCl2.The morphology,size and size distribution of the particles were studied by transmission electron microscopy and dynamic light scattering.Dispersion destabilization of the colloidal copper oxide nanoparticles was detected by a Turbiscan apparatus.CuO/γ-Al2O3 catalysts were prepared by dispersing highly stable CuO nanoparticles on γ-alumina by mechanical stirring.The catalysts were analyzed by scanning electron microscopy,transmission electron microscopy,X-ray photoelectron,and X-ray diffraction,which confirmed the uniform dispersion of CuO on the support.The reduction of the nitro aromatic compounds,4-nitrophenol,3-nitrophenol,and 2-nitrophenol,were studied.The CuO/γ-Al2O3 catalysts were active for the reduction of these nitro aromatic compounds.     

Novel route to synthesize CuO nanoplatelets

A new synthesis route to obtain high-purity cupric oxide, CuO, using the hydrothermal reaction of copper sulfide and a NaOH solution in an oxygen atmosphere has been developed. The synthesized products showed nanoplatelet-like morphologies with rectangular cross-sections and dimensions at the nanometric scale. Variations in the oxygen partial pressure and synthesis temperature produced changes in size and shape, being found that the proliferation of nanoplatelet structures occurred at 200 °C and 30 bar.     

Parametric study on electrochemical deposition of copper nanoparticles on an ultrathin polypyrrole film deposited on a gold film electrode

Monoshaped and monosized copper nanostructured particles have been prepared by potentiostatic electrochemical deposition on an ultrathin polypyrrole (PPY) film, electrochemically grown on a Si(100) substrate sputter-coated with a thin gold film or gold-film electrode (GFE). The crystal size and the number density of the copper nanocrystals have been examined by varying several deposition parameters, including the thickness of the gold film, the PPY film thickness, the applied potential, and the Cu2+ and the electrolyte concentrations for copper deposition. Optimal conditions for uniform growth ofnanocrystals well-dispersed on the GFE have been determined, along with insight into the mechanism of crystal growth. A minimum gold film thickness of 80 nm is required to eliminate the effects of the gold-silicon interface. The PPY film thickness and homogeneity principally affect the shape uniformity of the nanocrystals, while the copper deposition potential could be used to regulate the size and number density of the nanocrystals. Both the Cu2+ and electrolyte concentrations are also found to play important roles in controlling the electrodeposition of nanocrystal growth.     

Influence of bath temperatures on the wettability of copper films surface prepared by electroless plating method on beech wood

Copper films were coated on beech wood substrates by electroless plating method. The influence of bath temperature on the copper films properties was studied by varying the bath temperatures 25, 35, 45 and 55 °C. Scanning electron microscopy (SEM) equipped with energy dispersive spectroscopy (EDS), X‐ray diffraction (XRD) pattern, X‐ray photoelectron spectroscopy (XPS), micro Raman spectroscopy and contact angle measurements were used to both characterize the physical and chemical copper films properties and understand the influence of bath temperature on the wettability of copper surface. In our studies, we have found that the gained copper mass significantly increased at 55 °C. The crystalline nature of the coated copper was confirmed by XRD. The presence of Cu₂O and CuO was observed by XPS and micro Raman techniques, which confirms the oxidization of the coated copper surface. Also these characterization techniques have shown the big influence of bath temperature on the morphology, grain size, chemical composition and the film thickness of the coated copper. The wettability was highly influenced by increasing CuO on the coated copper, which is increased by the bath temperature. The contact angle measurements have demonstrated the influence of C―O, O―C?O and CuO components of the surface on the wettability of the samples. Copyright © 2016 John Wiley & Sons, Ltd.     

多孔氧化铜空心微球的一步法制备及其光催化性能

采用一步法成功制备出多孔氧化铜空心微球,用SEM、XRD和FTIR对制得的样品进行了表征。研究发现,碳源、反应温度、反应时间、CuSO4浓度等实验条件在多孔微球的制备过程中起着重要作用。在实验结果的基础上,提出了多孔氧化铜空心微球的形成机理。制备的多孔氧化铜空心微球的比表面积为409 m2.g-1,平均孔径为3.15 nm,总孔体积为0.256 cm3.g-1,这种空心微球具有量子尺寸效应并对罗丹明B有较高的光催化性能。     

Synthesis of Barium Lithium Fluoride Nanocrystals Using Reverse Micelles as Microemulsion

Barium lithium fluoride nanocrystals were synthesized in cetyltrimethylammonium bromide (CTAB)/2-octanol/water microemulsion systems. The impurity peaks in XRD patterns were not determined. The result of SEM confirmed that the average sizes and shape of the BaLiF3 nanocrystals. The formation of BaLiF3 and particles size were strongly affected by water content. With increasing water content and reaction times, the size of the particle increases.Meanwhile, the solvent was also found to play a key role in the synthesis of the BaLiF3 nanocrystals.     

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。     

Shape-controlled synthesis of copper colloids with a simple chemical route

The new electrical and optical properties of nanomaterials depend sensitively on both size and shape, which are of both fundamental and technological interest. This paper introduces a simple chemical method to produce copper particles, which has the ability to shape the particle without using any capping agent or template. In our synthetic procedure, the reactant concentration and temperature exerted a strong influence on the shape of the copper particles. At low reactant concentrations, the particles were cubic; at high reactant concentrations, obtained particles were spherical. The number of hollow particles greatly increased when the synthesis was performed at low temperature. We also synthesized a copper cubic ring at lower temperature, and it has been rarely reported. The absorption spectrum of hollow particles showed obvious red shifts, which suggests the possible assembly of novel optical materials.     

室温交联型硅丙微胶乳的合成研究II.改性微胶乳的粒径控制及其微观形态表征

采用种子微乳液聚合法和单体预乳化法分别合成了室温交联型有机硅改性聚丙烯酸酯微胶乳,研究了硅烷单体的添加和氨化反应对改性微胶乳粒子大小及分布的影响。结果表明:采用种子微乳液聚合法得到的硅丙微胶乳粒子大小与硅烷单体的种类、用量和添加顺序无关,平均粒径约为40~60nm。TEM照片显示出,采用种子微乳液聚合法合成的硅丙微胶乳粒子由于内部存在交联结构而导致表面形状不规则,有“乳突”现象;而采用预乳化法合成的硅丙微胶乳粒径粗大,呈规则的球形,氨化后粒径从100nm以上减小到80nm左右,粒子表面出现“绒毛”现象,这是由于硅烷组分的水解反应受到抑制而使粒子内部的交联密度降低的缘故。     

Polyhedral gold nanocrystals with O h symmetry: from octahedra to cubes

We report the shape and size control of polyhedral gold nanocrystals by a modified polyol process. The rapid reduction of gold precursors in refluxing 1,5-pentanediol has successfully provided a series of gold nanocrystals in the shape of octahedra, truncated octahedra, cuboctahedra, cubes, and higher polygons by incremental changes of silver nitrate concentration. All nanocrystals were obtained quantitatively and were uniform in shape and size in the range of approximately 100 nm. Smaller octahedra and cubes were also prepared by using large amounts of PVP. Silver species generated from AgNO3 seemed to determine the final nanocrystal morphology by the selective growth of {111} and/or the restriction of {100}. The shape evolution of the particles was addressed by quenching the reactions at different time intervals. The approximately 60 nm seeds were generated rapidly and grown slowly with simultaneous edge sharpening. Aging the reaction mixture focused the size and shape of the nanocrystals by Ostwald ripening. We believe that our selective growth conditions can be applied to other shapes and compositions of face-centered cubic metals.