Solvothermal synthesis of well-dispersed NaMgF3 nanocrystals and their optical properties

Complex metal fluoride NaMgF(3) nanocrystals were successfully synthesized via a solvothermal method at a relatively low temperature with the presence of oleic acid, and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) spectra, photoluminescence (PL) excitation and emission spectra, respectively. In the synthetic process, oleic acid as a surfactant played a crucial role in confining the growth and solubility of the NaMgF(3) nanocrystals. The as-prepared NaMgF(3) nanocrystals have quasi-spherical shape with a narrow distribution. A possible formation mechanism of the nanocrystals was proposed based on the effect of oleic acid. The as-prepared NaMgF(3) nanocrystals are highly crystalline and well-dispersed in cyclohexane to form stable and clear colloidal solutions, which demonstrate a strong emission band centered at 400 nm in photoluminescence (PL) spectra compared with the cyclohexane solvent. The PL properties of the colloidal solutions of the as-prepared nanocrystals can be ascribed to the trap states of surface defects.     

Arresting butterfly-like intermediate nanocrystals of beta-Co(OH)2 via ethylenediamine-mediated synthesis

A synthesis of beta-Co(OH)2 nanocrystalline materials has been investigated with the assistance of chelating agent ethylenediamine. By controlling precipitation processes, various forms of beta-Co(OH)2 crystallites can be prepared at different stages. The crystallite morphologies include two-dimensional hexagonal sheet platelets, one-dimensional nanorods, and butterfly-like nanocrystallite intermediates. In particular, a triangular construction unit for beta-Co(OH)2 crystallites has been revealed with the ethylenediamine mediation in the synthesis. With the successful arrest of these butterfly-like intermediate crystallites, especially of linearly aligned "butterflies", the formation mechanism of one-dimensional nanorods or nanoribbons has been experimentally explained. The chemical composition of solution precursors and resultant beta-Co(OH)2 crystallites has been analyzed with UV-vis/FTIR/CHN /XRD/TGA/TEM/SAED methods. The relationships among various observed crystallite morphologies have also been discussed on the basis of the experimental findings.     

声场对水合氧化锆凝胶特性的影响

氧化锆具有良好的光学、热学、电学和机械性质[1],氧化锆纳米粉体是制备高性能氧化锆陶瓷的主要材料。溶胶 凝胶法是制备氧化锆纳米粉体的方法之一[2],避免形成硬团聚体是一个关键问题。水合氧化锆干凝胶中非架桥羟基是粉末产生硬团聚体的根源[2]。将超声波应用到溶胶 凝胶过程中可以改变硅凝胶的结构[3],本文对声扬作用下水合氧化锆凝胶的形貌、热特性以及红外吸收光谱等进行分析,研究声场对水合氧化锆凝胶特性的影响,以探讨声场减少硬团聚体形成的机理。1　实验部分1 1　主要仪器日本JEM 100CXII型透射电子显微镜,加速电压200kV;…     

Low-temperature synthesis of hexagonal (Wurtzite) ZnS nanocrystals

We report a low-temperature (150 degrees C) and simple synthesis of quasi-monodispersed and uniform hexagonal (Wurtzite) ZnS nanocrystals in ethylene glycol medium. The samples structures were characterized with X-ray diffraction technique and transmission electron microscopy. It is believed that ethylene glycol medium plays a key role in forming hexagonal ZnS which is a stable phase at high temperatures.     

Colloidal synthesis and self-assembly of CoPt(3) nanocrystals

Reduction of platinum acetylacetonate and thermodecomposition of cobalt carbonyl in the presence of 1-adamantanecarboxylic acid were employed in different coordinating mixtures to produce monodisperse, highly crystalline CoPt(3) nanoparticles. The mean particle size can be varied from 1.5 to 7.2 nm by controlling the reaction conditions and the type of coordinating mixture. As-synthesized CoPt(3) particles represent single crystal domains and have chemically disordered face-centered cubic (fcc) structure. Nearly spherical CoPt(3) nanocrystals were found to assemble into two- (2D) and three-dimensional (3D) structures. An AB(5) type superlattice is observed by TEM after mixing two nanoparticle samples with different mean sizes. Slow precipitation led to the formation of facetted colloidal crystals with sizes up to 20 microm.     

Photocatalytic degradation of 2,4-dichlorophenoxiacetic acid and 2,4,6-trichlorophenol with ZrO2 and Mn/ZrO2 sol-gel materials

Because of its semiconductor properties, sol-gel zirconia can be used as a photocatalyst. When zirconia is doped with transition metals, its electronic properties are modified. In this work, sol-gel Mn/ZrO₂ and ZrO₂ materials were tested for photocatalytic degradation of 2,4-dichlorophenoxiacetic acid and 2,4,6-trichlorophenol. The powders were characterized by XRD, UV-Vis and Raman spectroscopy. The apparent rate constants were calculated assuming pseudo-first order kinetics. The results reveal that ZrO₂ is effective as a photocatalyst; moreover, its photocatalytic properties improve when it is doped with manganese.     

Facile synthesis of silver chalcogenide (Ag2E; E=Se, S, Te) semiconductor nanocrystals

A general, one-pot, single-step method for producing colloidal silver chalcogenide (Ag(2)E; E = Se, S, Te) nanocrystals is presented, with an emphasis on Ag(2)Se. The method avoids exotic chemicals, high temperatures, and high pressures and requires only a few minutes of reaction time. While Ag(2)S and Ag(2)Te are formed in their low-temperature monoclinic phases, Ag(2)Se is obtained in a metastable tetragonal phase not observed in the bulk.     

Controlled synthesis and self-assembly of highly monodisperse Ag and Ag(2)S nanocrystals

A facile method to control the synthesis and self‐assembly of monodisperse Ag and Ag₂S nanocrystals with a narrow‐size distribution is described. Uniform Ag nanoparticles of less than 4 nm were obtained by thermolysis of Ag–oleate complexes in the presence of oleic acid and dodecylamine, and monodisperse Ag nanoparticles of less than 10 nm were also prepared in one step by using dodecylamine and oleic acid as capping agents. Moreover, the surface‐enhanced Raman scattering (SERS) properties of the Ag substrates have also been investigated. It is worth mentioning that these Ag nanoparticles and assemblies show great differences in the SERS activities of Rhodamine B dye. In addition, the superlattices of Ag₂S nanocrystals were synthesized with Ag–oleate complexes, alkanethiol, and sulfur as the reactants. The resulting highly monodisperse nanocrystals can easily self‐assemble into interesting superstructures in the solution phase without any additional assembly steps. This method may be extended to the size‐controlled preparation and assembly of many other noble‐metal and transition‐metal chalcogenide nanoparticles. These results will aid the study of the physicochemical properties of the superlattice assemblies and construction of functional macroscopic architectures or devices.     

High-yield synthesis and characterization of 1,2-bis(p-vinylphenyl)ethane

The quantitative synthesis and complete characterization of 1,2-bis(p-vinylphenyl)ethane (p,p-BVPE) and its meta-, para-mixed isomers are reported. These crosslinkers copolymerize randomly with p-methylstyrene, leading to random crosslink distributions. The crosslinkers are prepared by Grignard coupling of (m,p)-vinylbenzyl chloride in tetrahydrofuran at low temperature to give the statistical mixture of m,m-, m,p-, and p,p-isomers in quantitative yield. Pure p-vinylbenzyl chloride is converted to pure p,p-BVPE. p,p-BVPE has also been separated from the mixture of isomers. The isomers are characterized by elemental analysis, mass spectrometry, ¹H-NMR, and ¹³C-NMR and by reversed-phase HPLC. © 1994 John Wiley & Sons, Inc.     

Role of surface coating in ZrO2/Eu3+ nanocrystals

The sol-emulsion-gel method is used for the preparation of Eu3+ ion-doped and coated ZrO2 nanocrystals. Here, we report the role of surface coating, dopant concentration, and temperature of heating in the modification of their crystal structure and photoluminescence properties. It is found that the volume fraction of the tetragonal phase increases from 28.08 to 91.56% because of surface coating. This is a significant modification of the crystal phase in ZrO2 nanocrystals due to surface coating by Eu2O3. It is found that the photoluminescence properties are sensitive to the crystal structure, which is again controlled by surface coating, concentration, and heating temperature. It is found that the decay time (tau) of Eu-doped ZrO2 nanocrystals increases with increasing the concentration of dopant and with increasing the temperature of heating because of changes in their crystal phase. The emission intensity of the peak at 611-617 nm (5D0 --> 7F2) of the Eu3+ ion-activated ZrO2 nanocrystals (doped and coated) is also found to be sensitive to the nanoenvironment. The average decay times are 770 and 488 mus for 1100 degrees C-heated 1.0 mol % Eu2O3-doped and coated ZrO2 nanocrystals, respectively. Our analysis suggests that the site symmetry of the ions plays the most important role in the modifications of the radiative and nonradiative relaxation mechanisms as a result of the overall photoluminescence properties.     

Sol-gel synthesis of dispersed ZrO2 nanoparticles

The influence exerted by the basicity of organic amines on hydrolytic polycondensation of zirconium tetraisopropoxide was studied in order to obtain nanodispersed ZrO₂ particles of various sizes.     

Shape-controlled synthesis of semiconducting CuFeS2 nanocrystals

Nanocrystals of the semiconducting chalcopyrite CuFeS₂ have been synthesized utilizing a facile solution-based method. Depending on the choice of precursors and synthesis conditions, the nanocrystals exhibit either a spherical (～12 nm) or pyramidal morphology (～30 nm), with a narrow size distribution. The band gap of the pyramidal nanocrystals is very close to the bulk value, but a larger band gap is obtained for the spherical nanocrystals likely because of size confinement effect.     

One-step synthesis of highly water-dispersible Mn(3)O(4) nanocrystals

Highly water-dispersible Mn(3)O(4) nanocrystals with well-controlled size, size distribution and high crystallinity have been successfully synthesized through a modified polyol process. Poly(acrylic acid) is used as the capping agent, conferring upon the particles high water-dispersion, of which the carboxylate groups partially bind to the nanocrystal surface and the uncoordinated carboxylate groups extend into water. The water-dispersible Mn(3)O(4) nanocrystals can be further transferred to nonpolar solvent by linking oleylamine molecules through electrostatic interaction. The as-prepared Mn(3)O(4) nanocrystals exhibit ferromagnetic behavior at low temperature and weak paramagnetic behavior at room temperature. The Curie-Weiss temperature and the blocking temperature are 40 K and 32 K, respectively.     

Thermal behaviour of amorphous Li2ZrO3 prepared by sol-gel technique

The results of the investigations of thermal behaviour of Li₂ZrO₃, prepared in the amorphous state by means of sol-gel technique are demonstrated. The thermal treatment was carried out in air under constant heating rate of 5 deg·min^–1 and cooling rate of 2.5 deg·min^–1. The methods of DTA, TG, Emanation Thermal Analysis (ETA) and dilatometry were used, for characterization of the thermal behaviour in dynamic conditions. The X-ray diffraction patterns were used for characterization of the phase changes observed by TA Methods.

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Zusammenfassung Ergebnisse aus Untersuchungen des thermischen Verhaltens von Li₂ZrO₃, hergestellt mittels einer Sol-Gel-Technik im amorphen Zustand werden dargelegt. Die thermische Behandlung wurde in Luft bei einer konstanten Aufheizgeschwindigkeit von 5 Grad·min^–1 und einer Abkühlgeschwindigkeit von 2,5Grad·min^–1 durchgeführt. Zur Beschreibung des thermischen Verhaltens unter dynamischen Verhältnissen wurden DTA, TG, Emanationsthermoanalyse und Dilatometrie angewendet. Zur näheren Charakterisierung der bei TG beobachteten Phasenumwandlungen wurde Röntgendiffraktion verwendet.

     

Selective synthesis of monazite- and zircon-type LaVO(4) nanocrystals

Pure monoclinic (m-) and tetragonal phased (t-) LaVO(4) nanocrystals could be obtained by a hydrothermal method in a controllable way with additives. It is found that chelating ligands, such as ethylenediaminetetraacetic acid [EDTA or H(4)L, where L(4-) = (CH(2)COO)(2)N(CH(2))(2)N(CH(2)COO)(2)(4-)], favor the formation of t-LaVO(4) and can induce the polymorph transformation from stable m-LaVO(4) to metastable t-LaVO(4). Further studies demonstrated the important roles of chelating ligands in this transformation process. Careful investigation over the phase transition from t- to m-LaVO(4) was also conducted with high-temperature X-ray diffraction (HTXRD) studies. The phase transition occurred at 850 degrees C, which is about 250 degrees C higher than for the bulk. The enhanced thermal stability of the nanosized metastable t-LaVO(4) may come from the small size effect. Our capability of obtaining and stabilizing t-LaVO(4) not only benefits the wider applications based on LaVO(4) due to the improved luminescent and catalytic performance but also provides a new idea in the studies of polymorph control and selective synthesis of inorganic materials.     

Novel synthesis of well-dispersed crystalline SnO2 nanoparticles by water-in-oil microemulsion-assisted hydrothermal process

Well-dispersed crystalline tin dioxide (SnO2) nanoparticles were synthesized by a novel and simple water-in-oil (w/o) microemulsion-assisted hydrothermal process, using low-cost tin chloride as the starting material. The typical quaternary microemulsions of cetyltrimethylammonium bromide (CTAB)/n-pentanol/n-hexane/water were used as space-confined microreactors for the nucleation, growth, and crystallization of SnO2 nanoparticles under hydrothermal conditions. The techniques of XRD, TEM, HRTEM, SAED, EDS, FTIR, XPS, and N2 adsorption measurement were used to characterize the compositions and structures of obtained samples. The results show that the SnO2 nanoparticles have high specific areas (107-169 m2 g(-1)), small particle sizes (ca. 3.0 nm), high crystallinity, and narrow size distributions. The well-dispersed, uniform, and well-crystallized powders with microporous texture are favorable for gas-sensing applications. The as-developed microemulsion-assisted in situ crystallizing process can be extended to prepare other oxide, metal, and sulfide nanoparticles.     

Concise synthesis of NaTi2(PO4)3 nanocrystals with size and morphology control

NaTi_2 (PO_4)_3 (NTP) nanocrystals with high room-temperature ionic conductivity of 1.1×10~3 S/cm were prepared by a concise solvothermal method at 140 ℃ for 3 h, and the aspect ratios of all the NTP nanocrystals are the closest to 0.7. It implies a moderate size-distribution of NTP nanocrystals obtained at 140 ℃ for 3 h is helpful for increasing packing density, and the packing density is the larger, so its conductivity is the higher. The controllability over size and morphology of the NTP nanocrystals via solvothermal temperature and time were investigated. The results suggest that our method is of great potential in synthesizing NTP nanocrystals with high room-temperature ionic conductivity at low cost.     

Photochromism of spiropyran nanocrystals embedded in sol-gel matrices

Spectroscopic and kinetic properties of a new photochromic medium, consisting of nanocrystals of spyropyran molecules (1,3-dihydro-1,3,3,5',6',pentamethyl-spiro[2H-indole-2,2'-[2H]pyrano [3,2-b]pyridinium] iodide) embedded in an organo-silicate sol-gel film, are presented and compared to microcrystals obtained by slow evaporation of a solvent. High photoconversion efficiencies for both kinds of crystals have been observed. In microcrystals, the photomerocyanine form absorbs at 570 nm with a fading rate of 5 h, in nanocrystals the photomerocyanine form absorbs at 535 nm with a fading rate of 41 h. Therefore, the crystalline structure of nanocrystals is different from the microcrystal one.     

The first synthesis of Pb(1-x)Mn(x)Se nanocrystals

In this work, Mn-doped PbSe nanocrystals (NCs) have been, for the first time, prepared through a high-temperature organic solution approach. To ensure that all the Mn2+ ions are indeed incorporated into the NCs and not only physically presented at the surface, Mn-Se prebonded precursor was selected, and a ligand-exchange process was also conducted before and after the synthesis, respectively. Various analyses including EDS, ICP, XRD, SQUID, and EPR confirm that the Mn2+ ions have been successfully doped into PbSe NCs.