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.     

Synthesis and characterization of cuprous selenide nanocrystals at room temperature

A simple method has been developed to prepare cuprous selenide nanocrystals by the reaction of copper nitrate trihydrate with selenium and sodium mercaptoacetate in aqueous ammonia system. Cu_2Se nanocrystals were characterized by transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), electron diffraction (ED), fluorescence spectrum and ultraviolet-visible absorption spectrum. Cu_2Se nanocrystals showed berzelianite structure with 20-40 nm in length and 10-20 nm in width. A possible mechanism is also discussed.     

Self-organized monolayer of nanosized ceria colloids stabilized by poly(vinylpyrrolidone)

Four nanometer colloidal ceria nanocrystals in a fluorite cubic structure have been synthesized via an alcohothermal treatment at 180 degrees C for 24 h from Ce(NO(3))(3)*6H(2)O in ethanol, using various alkylamines including triethylamine, butylamine, and hexadecylamine as the bases and poly(vinylpyrrolidone) (PVP) as the stabilizer. They were characterized by multiple measurements of X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), ultraviolet visible (UV-vis) spectroscopy, dynamic light scattering (DLS), and infrared spectroscopy (IR). The introduction of PVP could effectively stabilize the cerium nuclei against self-aggregation and finally lead to the formation of the CeO(2) colloids. As compared with that of their precipitated counterparts, the UV-vis spectra showed a blue-shifted absorption edge for the as-obtained colloidal nanocrystals, revealing that their surfaces were well-passivated by PVP. Four types of self-organized monolayer patterns (i.e., isolated particles, short chainlike (pseudo-1-D aggregated), pearl necklace-like (1-D aggregated), and dendritic (pseudo-2-D aggregated) alignments) appeared for the as-obtained colloidal particles on the copper TEM grids, due to the delicate balance of the attractive and repulsive forces between the PVP-passivated CeO(2) nanocrystals during the irreversible evaporation of the solvent from various colloidal solutions under ambient conditions. The type of alkylamine and the concentration of PVP were confirmed to be the crucial factors determining the oriented-aggregation dimensionality of the CeO(2) colloids. Possible interparticle interaction modes have been suggested to explain such complex self-organization patterns exhibited by the as-obtained CeO(2) nanocrystals.     

Improved antibacterial activity of HAP garlanded PLGA ultrafine fibers incorporated with CuO: synthesis and characterization

Well-organized nanocrystalline hydroxyapatite nanoparticles garlanded poly(dl-lactide-co-glycolide) (PLGA) ultrafine fibers with efficient antibacterial properties are of great interest in the development of new products. In the present study, hydroxyapatite doped PLGA ultrafine fibers incorporated with copper oxide nanocrystals were fabricated via two step methodology. Primarily; copper oxide nanocrystals were synthesized using wet chemical method. Then the as-synthesized nanocrystals were used for the preparation of composite fibers using electrospinning technique. The properties of pure and composite ultrafine fibers were characterized using X-ray diffraction, scanning electron microscopy, energy dispersive X-ray analysis, and electron probe mapping analysis. The in vitro antimicrobial activity of synthesized pure and hydroxyapatite doped PLGA ultrafine fibers was investigated against model organism Escherichia coli (gram negative) using optical density method and morphological damage was observed by TEM. Ultrafine fibers with average diameter ranges from 1.0 to 1.2 μm were obtained. Uniform distribution of hydroxyapatite was observed. Admirable antimicrobial activity against E. coli was achieved which could be attributed by the synergy between hydroxyapatite and copper oxide. In contrast to pristine PLGA, lower concentrations of hydroxyapatite–copper oxide doped PLGA nanocomposite were needed to strongly inhibit the growth of E. coli. Our results report successful preparation of hydroxyapatite–copper oxide based novel nanocomposite. The developed hybrid nanocomposite possess exceptionally good antibacterial activity against E. coli due to the synergistic effect of hydroxyapatite and copper oxide. The antimicrobial nanocomposite can be utilized for a range of bio-functional purposes such as a good candidate for water purification, antibiofouling, wound dressings and bone tissue engineering etc.     

Size-controlled chalcopyrite CuInS2 nanocrystals: One-pot synthesis and optical characterization

Chalcopyrite ternary CuInS2 semiconductor nanocrystals have been synthesized via a facile one-pot chemical approach by using oleylamine and oleic acid as solvents.The as-prepared CuInS2 nanocrystals have been characterized by instrumental analyses such as X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS),transmission electron microscopy(TEM)/high-resolution TEM(HRTEM),energy-dispersive X-ray spectroscopy(EDS),UV-vis absorption spectroscopy(UV-vis) and photoluminescence(PL) spectroscopy.The particle sizes of the CuInS2 nanocrystals could be tuned from 2 to 10 nm by simply varying reaction conditions.Oleylamine,which acted as both a reductant and an effective capping agent,plays an important role in the size-controlled synthesis of CuInS2 nanocrystals.Based on a series of comparative experiments under different reaction conditions,the probable formation mechanism of CuInS2 nanocrystals has been proposed.Furthermore,the UV-vis absorption and PL emission spectra of the chalcopyrite CuInS2 nanocrystals have been found to be adjustable in the range of 527-815 nm and 625-800 nm,respectively,indicating their potential application in photovoltaic devices.     

Luminescence of Polyethylene Glycol Coated CdSeTe/ZnS and InP/ZnS Nanoparticles in the Presence of Copper Cations

The use of click chemistry for quantum dot (QD) functionalization could be very promising for the development of bioconjugates dedicated to in vivo applications. Alkyne–azide ligation usually requires copper(I) catalysis. The luminescence response of CdSeTe/ZnS nanoparticles coated with polyethylene glycol (PEG) is studied in the presence of copper cations, and compared to that of InP/ZnS QDs coated with mercaptoundecanoic acid (MUA). The quenching mechanisms appear different. Luminescence quenching occurs without any wavelength shift in the absorption and emission spectra for the CdSeTe/ZnS/PEG nanocrystals. In this case, the presence of copper in the ZnS shell is evidenced by energy‐filtered transmission electron microscopy (EF‐TEM). By contrast, in the case of InP/ZnS/MUA nanocrystals, a redshift of the excitation and emission spectra, accompanied by an increase in absorbance and a decrease in photoluminescence, is observed. For CdSeTe/ZnS/PEG nanocrystals, PL quenching is enhanced for QDs with 1) smaller inorganic‐core diameter, 2) thinner PEG shell, and 3) hydroxyl terminal groups. Whereas copper‐induced PL quenching can be interesting for the design of sensitive cation sensors, copper‐free click reactions should be used for the efficient functionalization of nanocrystals dedicated to bioapplications, in order to achieve highly luminescent QD bioconjugates.     

Cu2SnSe3-Ag纳米复合物的合成及其热电性质研究

采用Schlenk line技术,通过一种简单的硒源热注射的方法合成了Cu_2SnSe_3(CTSe)纳米晶,同时采用胶体法得到了单分散性极好的、粒径为4nm左右的Ag纳米颗粒(Ag NPs),之后通过简单的滴加法向CTSe纳米晶基质中掺入了特定比例的Ag NPs,得到CTSe-Ag纳米复合物。通过X射线粉末衍射、透射电镜、高分辨透射电镜、红外光谱和热重分析等表征了样品的组成、结构和形貌。同时对合成样品的热电性质进行了研究,相关的测试结果表明,以CTSe为基体掺杂AgNPs的样品中,CTSe-1(mol)%Ag具有最佳的热电优值(ZT=0.23,655K),相较纯相CTSe(ZT=0.18,655K)提高了27%。     

表面活性剂控制的硒纳米线的室温生长

以表面活性剂十二烷基硫酸钠(SDS)为形貌导向剂,利用Na₂Se在室温碱性水溶液中的自发氧化,成功制备了Se纳米线。用TEM、SEM、EDX、XRD、HRTEM、SEAD等手段表征了Se纳米线的组成和结构。结果表明,合成的Se纳米线是沿六方相Se的[001]轴方向生长,具有良好的晶型结构。使用TEM对不同时间Se纳米结构的生长过程的形貌进行了跟踪,探讨了Se纳米线的形成机理,发现其形成与生长过程符合“solid-solution-solid”机理。同时,选择了具有特异官能团(如-OH,-COOH,-CONH₂)的3种表面活性剂,研究它们在纳米硒的取向性生长中的导向作用,只有SDS能引导合成出高质量的Se纳米线。     

Facile synthesis of nanocrystalline wurtzite Cu-In-S by amine-assisted decomposition of precursors

Phase-pure ternary wurtzite Cu-In-S nanocrystals have been synthesized by a simple amine-assisted decomposition of mixed precursor complexes derived from S-methyl dithiocarbazate (SMDTC) at a relatively low temperature without using any external surfactant. The crystal phase, morphology, crystal lattice, and chemical composition of the as-prepared products were analyzed by using X-ray diffraction, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and energy-dispersive X-ray spectroscopy (EDX). The optical properties show the pronounced quantum confinement effect in nanocrystals. A possible growth mechanism has been suggested for the formation of anisotropic wurtzite Cu-In-S It is believed that a combined effect of the chelating amine and precursors containing CH₃S unit plays a key role in the formation of the metastable phase of wurtzite Cu-In-S.     

Synthesis of Cu3Sn Alloy Nanocrystals through Sequential Reduction Induced by Gradual Increase of the Reaction Temperature

Cu₃Sn alloy nanocrystals are synthesized by sequential reduction of Cu and Sn precursors through a gradual increase of the reaction temperature. By transmission electron microscopy (TEM), energy‐dispersive X‐ray spectroscopy (EDS), UV/Vis spectroscopy, and X‐ray diffraction (XRD) analyses, the alloy formation mechanism of Cu₃Sn nanocrystals has been studied. The incremental increase of the reaction temperature sequentially induces the reduction of Sn, the diffusion of Sn into the preformed Cu nanocrystals, resulting in the intermediate phase of Cu–Sn alloy nanocrystals, and then the formation of Cu₃Sn alloy nanocrystals. We anticipate that the synthesis of Cu₃Sn alloy nanocrystals encourages studies toward the synthesis of various alloy nanomaterials.     

Single‐Crystalline and Near‐Monodispersed NaMF3 (M=Mn,Co, Ni,Mg) and LiMAlF6 (M=Ca,Sr) Nanocrystals from Cothermolysis of Multiple Trifluoroacetates in Solution

We report the synthesis of single‐crystalline and near‐monodispersed NaMF₃ (M=Mn, Co, Ni, Mg), LiMAlF₆ (M=Ca, Sr), and NaMgF₃:Yb,Er nanocrystals (quasisquare nanoplates, nanorods, and nanopolygons) by the cothermolysis of multiple trifluoroacetates in hot combined organic solvents (oleic acid, oleylamine, and 1‐octadecene). The nanocrystals were characterized by XRD, TEM, superconductive quantum interference device (SQUID), and upconversion luminescence spectroscopy. By regulating the polarity of the dispersant, the NaMF₃ (M=Mn, Co, Ni) nanoplates were partially aligned to form nanoarrays on copper TEM grids. The sizes of the NaMF₃ nanocrystals were easily tuned by the use of proper synthetic conditions such as reaction temperature and time and solvent composition. On the basis of a series of experiments in which the reaction conditions were varied, together with GC–MS and FTIR analysis, the reaction pathways for the formation of these nanocrystals from trifluoroacetate precursors were proposed. The magnetic measurements showed that the differently sized NaMnF₃ square plates displayed interesting weak ferromagnetic behavior on the nanometer scale. The strong red upconversion luminescence emitted from the NaMgF₃:Yb,Er nanorods under 980‐nm near‐IR laser excitation suggests that NaMgF₃ may be a good candidate host material for red upconversion luminescence.     

Deciphering Ligands’ Interaction with Cu and Cu2O Nanocrystal Surfaces by NMR Solution Tools

The hydrogenolysis of [Cu₂{(iPrN)₂(CCH₃)}₂] in the presence of hexadecylamine (HDA) or tetradecylphosphonic acid (TDPA) in toluene leads to 6–9 nm copper nanocrystals. Solution NMR spectroscopy has been used to describe the nanoparticle surface chemistry during the dynamic phenomenon of air oxidation. The ligands are organized as multilayered shells around the nanoparticles. The shell of ligands is controlled by both their intermolecular interactions and their bonding strength on the nanocrystals. Under ambient atmosphere, the oxidation rate of colloidal copper nanocrystals closely relies on the chemical nature of the employed ligands (base or acid). Primary amine molecules behave as soft ligands for Cu atoms, but are even more strongly coordinated on surface Cu^I sites, thus allowing a very efficient corrosion protection of the copper core. On the contrary, the TDPA ligands lead to a rapid oxidation rate of Cu nanoparticles and eventually to the re‐dissolution of Cu^II species at the expense of the nanocrystals.     

Assembly of heteropoly acid nanoparticles in SBA-15 and its performance as an acid catalyst

Keggin‐type 12‐tungstophosphoric acid (TPA) nanocrystals have been assembled inside the pores of mesoporous silica through a vacuum impregnation method by using large‐pore SBA‐15 as a nanoreactor. The product was characterized by Brunauer–Emmet–Teller particle size distribution (BET‐PSD), NMR and FT‐IR spectroscopy, X‐ray diffraction (XRD), tranmsission electron microscopy (TEM), differential thermal analysis (DTA) and FT‐IR of adsorbed pyridine. The experimental results illustrate that the TPA nanocrystals are excellent Brønsted acid catalytic materials at room temperature.     

Synthesis and structural characterization of sol–gel derived titania/poly (vinyl pyrrolidone) nanocomposites

Non hydrolytic sol–gel method was employed to synthesize pure anatase TiO₂ nanocrystals using tetra isopropyl orthotitanate and poly vinylpyrrolidone as precursors. The structural analyses of the prepared samples were carried out using Fourier transform infrared spectroscopy (FT-IR), thermo gravimetric and differential thermal analysis (TG–DTA), X-ray diffraction (XRD), Raman spectroscopy, transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDS). The capping of PVP around TiO₂ nanoparticles was confirmed by FT-IR spectroscopy, the interaction being via bridging oxygens of the carbonyl (C=O) and the nanoparticle surface. The XRD, Raman and TEM results indicate that the prepared samples had a pure anatase nano-TiO₂ structure. The particle size analysed by TEM ranged between 7 and 12 nm. The size of the nanocrystals evaluated from the XRD spectra and TEM micrograph is well in agreement. The spacing for the crystal planes was also determined using the ImageJ program applied to the TEM micrographs.     

Mn3O4多面体纳米晶体的制备及其电化学性能

通过对未加添加剂的醋酸锰-乙醇体系的一种简易的水基热解过程,制备了Mn3O4多面体纳米晶体。借助X射线衍射仪(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、傅里叶变换红外光谱法(FTIR)、拉曼光谱和X-射线光电子能谱(XPS)等对Mn3O4的结构和形貌进行了表征。提出了Mn3O4多面体纳米晶体的形成机理。循环伏安法(CV)测试结果表明,所制得的Mn3O4电极呈现良好的赝电容性能。在扫描速率为5 mV.s-1时,得到了Mn3O4的最大比电容值173 F.g-1。     

Preparation of Monodispersed Copper Nanoparticles by an Environmentally Friendly Chemical Reduction

In this paper, highly dispersive nanosized copper particles with a mean particle size of less than 6 nm are prepared by an environmentally friendly chemical reduction method. Non-toxic L-ascorbic acid acts as both reducing agent and antioxidant in ethylene glycol in the absence of any other capping agent. Transmission electron microscopy （TEM） is used to characterize the size and morphology of Cu nanoparticles. The results of UV-Vis spectroscopy （UV-Vis）, energy dispersive spectroscopy （EDS） and high resolution TEM （HRTEM） illustrate that the resultant product is pure Cu nanocrystals. The size of Cu nanoparticles is remarkably impacted by the order of reagent addition, and the investigation reveals the reaction procedure of Cu^2＋ ions and L-ascorbic acid.     

ZnSe;Cu纳米晶/聚电解质多层膜制备和结构研究

采用分子沉积方法制备了ZnSe;Cu纳米晶/聚电解质多层膜,通过X射线光电子能谱(XPS)和透射电镜(TEM)等方法对薄膜的组成及结构进行了表征.XPS结果证实了回流处理对ZnSe;Cu微粒的表面结构以及铜离子价态的影响,从而很好地解释了经表面修饰后,微粒荧光增强的现象.TEM结果确定ZnSe;Cu的平均尺寸为3nm.X射线粉末衍射结果进一步确认ZnSe;Cu具有纤锌矿晶体结构.     

Site-selective direct photochemical deposition of copper on glass substrates using TiO2 nanocrystals

Deposition of copper thin films was achieved by a photocatalytic reaction of site-selectively adsorbed TiO(2) nanocrystals for direct fabrication of copper circuit patterns on glass substrates. The nanocrystal monolayers absorbed on hydrophobic surface templates serve as an effective photocatalyst, producing metallic copper and formic acid via oxidation of methanol in solution. The formic acid generated has also been suggested to serve as an electron donor that accelerates copper deposition through a UV-mediated autocatalytic reaction, even after nanocrystals are embedded into the grown copper films. The thickness of the deposited copper films was easily controlled by varying the UV irradiation time, irradiation power, and initial concentration of methanol as a hole scavenger. The process presented herein provides an effective methodology for resist-free, direct metallization of insulating substrates.     

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.

     

Enhanced Magneto‐optical Properties of Semiconductor EuS Nanocrystals Assisted by Surface Plasmon Resonance of Gold Nanoparticles

Remarkable magneto‐optical properties of a new isolator material, that is, europium sulfide nanocrystals with gold (EuS–Au nanosystem), has been demonstrated for a future photo‐information technology. Attachment of gold particles that exhibit surface plasmon resonance leads to amplification of the magneto‐optical properties of the EuS nanocrystals. To construct the EuS–Au nanosystems, cubic EuS and spherical Au nanocrystals have been joined by a variety of organic linkers, that is, 1,2‐ethanedithiol (EDT), 1,6‐hexanedithiol (HDT), 1,10‐decanedithiol (DDT), 1,4‐bisethanethionaphthalene (NpEDT), or 1,4‐bisdecanethionaphthalene (NpDDT) . Formation of these systems was observed by XRD, TEM, and absorption spectra measurements. The magneto‐optical properties of the EuS–Au nanosystem have been characterized by using Faraday rotation spectroscopy. The Faraday rotation angle of the EuS–Au nanosystem is dependent on the Au particle size and interparticle distance between EuS and Au nanocrystals. Enhancement of the Faraday rotation of EuS–Au nanosystems was observed. The spin configuration in the excited state of the EuS–Au nanosystem was also investigated using photo‐assisted electron paramagnetic resonance.