Solvothermal synthesis and characterization of uniform CdS nanowires in high yield

Large-scale CdS nanowires with uniform diameter and high aspect ratios were synthesized using a simple solvothermal route that employed CdCl₂ and S powder as starting materials, ethylenediamine (en) as the solvent. X-ray diffraction (XRD) pattern and transmission electron microscopy (TEM) images show that the products are hexagonal structure CdS nanowires with diameter of 40 nm and length up to 10 μm. Selected area electron diffraction (SAED) and high resolution TEM (HRTEM) studies indicate the single-crystalline nature of CdS nanowires with an oriented growth along the c-axis direction. The optical properties of the products were characterized by optical absorption spectra and photoluminescence spectra. Based on the results of contrastive experiments, it is found that the sulfur source and the solvent play significant roles in the formation of uniform nanowires. A possible formation mechanism of nanowires is discussed.     

Large single crystals of colloidal silica spheres appearing in deionized and diluted suspension

Close-up color photographs are taken for crystallites (single crystals surrounded by the grain boundaries) in the colloidal crystals of monodisperse silica spheres (diameter: 110 nm±4.5 nm (standard deviation)). Very large crystallites (34 mm) are observed with the naked eye (for the first time) for the completely deionized and diluted suspensions. Deionization is carefully made with the mixed beds of ion-exchange resins more than 2 weeks old. Size of the crystallites increases sharply as the concentration of spheres decreases, and becomes small at the concentrations slightly higher than the critical concentration of melting toward liquid-like structure. Shape of the crystallites, i.e., mixture of triangle, cubic, pentagonal, hexagonal, cone-like, etc., is recognized in the photographs.     

Structural and dynamic properties of colloidal liquids and gases of silica spheres (29 nm in diameter) as studied by the light scattering measurements

Static and dynamic light-scattering measurements are made for colloidal-liquids and -gases of silica spheres (29 nm in diameter) in the exhaustively deionized aqueous suspension and in the presence of sodium chloride. Single broad peak is observed in the light-scattering curve and the liquid-like and gas-like distributions have been observed. Colloidal crystals are not formed at any sphere concentrations. The nearest-neighbored interparticle distances of colloidal liquids, l _obs , agree excellently with the effective diameters of spheres (d _eff ) including the electrical double layers in the effective soft-sphere model and also with the mean intersphere distances, l _o , calculated from the sphere concentration, i.e., l _obs ≈d _eff ≈ l _o . This relation supports the importance of the electrostatic interparticle repulsive interaction. Two dynamic processes have been extracted separately from the time profiles of autocorrelation function of colloidal liquids. Decay curves of colloidal gases are characterized by the single translational diffusion coefficients, which are always lower than the calculation from the Stokes-Einstein equation using true diameter of spheres and increase as ionic concentration increases. These experimental results emphasize the importance of the expanded electrical double layers and the electrostatic intersphere repulsion on the structural and dynamic properties of the colloidal liquids and gases. Electronic Publication     

Drying dissipative patterns of colloidal crystals of silica spheres in organic solvents

Drying dissipative structural patterns formed in the course of drying colloidal crystals of silica spheres (110 nm in diameter) in water, methyl alcohol, ethyl alcohol, 1-propyl alcohol, diethyl ether, and in the mixtures of ethyl alcohol with the other solvents above have been studied on a cover glass. The macroscopic broad rings were formed in the outside edges of the dried film for all the solvents examined. Furthermore, much distinct broad rings appeared in the inner area when the solvents were ethyl alcohol, methyl alcohol, and their mixtures. Profiles of the thickness of the dried films were sensitive to the organic solvents and explained well with changes in the surface tensions, boiling points, and viscosities of the solvents. The macroscopic and microscopic spoke-like crack patterns formed. The drying area (or the drying time) increased (or decreased) as the surface tension of the solvent decreased. However, the absolute values of these drying parameters are determined also by the boiling points of the solvents. Importance of the fundamental properties of the solvents is supported in addition to the characteristics of colloidal particles in the drying dissipative pattern formation.     

Phase diagram of alloy crystal in the exhaustively deionized suspensions of binary mixtures of colloidal spheres

Phase diagrams of liquidlike, alloy crystal-like and amorphous solid-like(AS) structures have been obtained for the exhaustively deionized aqueous suspensions of the binary mixtures of polystyrene or silica spheres. Diameter, polydispersity index (standard deviation of diameter divided by the mean diameter) and size ratio of the binary spheres (diameter of small sphere divided by that of large one) range from 85 to 136 nm, 0.07 to 0.26 and 0.76 to 0.93, respectively. Close-up color photographs of the alloy crystals are taken and the crystal structure has been analysed from reflection spectroscopy. Most of the alloy crystals aresubstitutional solid-solution (sss) type and body-contered cubic lattice structure. Formation of the alloy crystals is attributed to the important role of the expanded electrical double layers in the deionized condition and increase toward unity in the effective size ratio, which is the effective diameter of small sphere including double layer divided by that of large sphere AS structure is formed at the rather high concentrations of two spheres, where the thickness of the electrical double layer is thin and the effective size rado is comparatively small.     

CdS纳米球的水热制备及性质表征

采用水热方法制备了CdS纳米球.通过扫描电镜和透射电镜可以看出:该方法可直接获得具有较好结构的纳米球,比较不同溶剂中得到产品的SEM,发现甘油对CdS纳米球的形成起到了重要的作用.X射线粉末衍射图谱中无杂质衍射峰出现,表明样品为纯的六方相CdS.CdS纳米球的室温光致发光光谱中有2个不同的峰.     

Preparation and optical properties of blue-emitting colloidal CdS nanocrystallines by the solvothermal process using poly (ethylene oxide) as the stabilizer

Blue-emitting colloidal CdS nanocrystals have been synthesized through the solvothermal reaction of cadmium acetate and thiourea in N,N-dimethylformamide using poly(ethylene oxide; PEO) as the stabilizing polymer. The as-prepared CdS colloids were stable at ambient conditions for several weeks. The PEO-stabilized CdS colloids showed a narrow fluorescence band with the maximum at about 420 nm and thus emitting blue fluorescence under the ultraviolet (UV) lamp. A common red shift of fluorescence band is not detected for the prepared CdS colloids in the study, indicating that PEO-stabilized CdS NCs possess few crystalline defects on their surface. In addition, transmission electron microscope micrographs reveal that the sizes of CdS NCs are between 4.4 to 5.4 nm with small standard deviations from 0.5 to 0.7 nm. The particle growth kinetics was studied by monitoring UV-visible absorption onsets versus the reaction time and was found to nearly follow the Lifshitz–Slyozov–Wagner theory for the Ostwald ripening mechanism.     

Sedimentation and drying dissipative patterns of binary suspensions of colloidal silica spheres having different sizes

The sedimentation and drying dissipative structural patterns were formed during the course of drying binary mixtures among colloidal silica spheres of 183 nm, 305 nm, and 1.205 μm in diameter in aqueous suspension on a watch glass, a glass dish, and a cover glass, respectively. The broad ring-like sedimentation patterns were formed within several hours in suspension state for all the substrates used. Colorful macroscopic broad ring-like drying patterns were formed for the three substrates. In a watch glass, macroscopic drying patterns were composed of the outer and inner layers of small and large spheres, respectively. The two colored layers were ascribed to the Bragg diffractions of light by the dried colloidal crystals of the corresponding spheres. The width ratio of the layers changed in proportion to the mixing ratio of each spheres. In a glass dish, wave-like macroscopic drying patterns were observed in the intermediate areas between the outside edges of the broad ring and the inner wall of the cell. On a cover glass, the sphere mixing ratios were analyzed from the widths of the drying broad rings of the small spheres at the outside edge. High and distinct broad rings of small spheres and the low and vague broad one formed at the outer edges and in the inner area, respectively. Drying dissipative pattern was clarified to be one of the novel analysis techniques of colloidal size in binary colloidal mixtures.     

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.     

Photoinduced variations in the size of nanoparticles of CdS in colloidal solutions

The possibility of decreasing the size of colloidal nanoparticles of CdS in the oxidative photocorrosion reaction in the presence of methylviologen and of increasing their size during photocatalytic reduction of sulfur in ethanol in the presence of cadmium acetate. A dependence of the quantum yield of the latter reaction on the initial size of CdS nanoparticles was observed, which was interpreted as a result of quantum size effects. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 43, No. 3, pp. 170–175, May–June, 2007.     

Dissipative structures formed in the course of drying the colloidal crystals of silica spheres on a cover glass

Macroscopic and microscopic dissipative structural patterns formed in the course of drying the deionized aqueous colloidal crystal suspensions of silica spheres (diameter: 103 nm) on a cover glass have been observed. Spoke-like and ring-like patterns are formed in the macroscopic scale; the former is the crack in the sphere film and the latter is the hill accumulated with spheres formed around the outside edge. The neighbored inter-spoke angle, thickness of the film, and other morphological parameters have been discussed as a function of sphere concentration, concentration of sodium chloride, and the inclined angle of the cover glass. Fractal patterns of the mud cracks are observed in the microscopic scale. Capillary forces between spheres at the air-liquid surface and the relative rates between the water flow at the drying front and the convection flow of spheres are important for the pattern formation. Electronic Publication     

Rigidity of colloidal crystals of silica spheres modified with polymers on their surfaces in organic solvents

Rigidity (G) of colloidal crystals in organic solvents of acetonitrile and nitrobenzene has been measured by reflection spectroscopy in sedimentation equilibrium. The colloidal spheres used are the silica spheres (136 nm in diameter) modified on their surfaces with polymers, poly(maleic anhydride-co-styrene) [P(MA-ST)], poly(methyl methacrylate) (PMMA), or polystyrene (PST). Log G increases linearly with the slope of unity as log N (number density of colloidal spheres) increases. The mean values of the b-factor, which is the fluctuation parameter in crystal lattices and should be smaller than 0.1 according to the Lindeman's rule, are 0.045±0.003, 0.039±0.007, and 0.038±0.003 for P(MA-ST)/SiO₂, PMMA/SiO₂, and PST/SiO₂, respectively. These values are larger than that of colloidal crystals of mother silica spheres in the deionized aqueous suspension, 0.028. These results support the important role of the excluded volume effects from the polymer layers formed around the silica surfaces. However, contribution of the excluded volume effects from the electrical double layers formed around the spheres in the organic solvents is also effective in the colloidal crystallization. Electronic Publication     

Kinetic study of the formation reaction of colloidal silica spheres in microgravity using aircraft

Polymerization reactions of colloidal silica spheres via the hydrolysis and dehydration processes of tetraethyl orthosilicate with ammonia and a tiny amount of water in ethyl alcohol have been studied in microgravity by the parabolic flights of a MU-300 rear-jet aircraft. Induction periods and polymerization rates are determined by fast-scanning transmitted-light-intensity measurements and the fast-scanning dynamic light-scattering method. Direct observation of the reaction mixtures is also made with a charge-coupled device video camera. Reproducible and reliable data are obtained in microgravity compared with those in gravity. Increases in the induction times and decreases in the polymerization rates are observed in microgravity compared with those in gravity. One of the main reasons for these observations is the fact that the translational Brownian movement of the reactants and/or product spheres is free from downward translational movement in microgravity. Very weak convection of the reaction suspensions in microgravity is another important factor. Received: 10 November 1998 Accepted in revised form: 12 January 1999     

溶剂热法制备MWNTs/CdS复合材料

分别以醋酸镉和硫脲为原料,二乙三胺和去离子水为混合溶剂,采用溶剂热技术制备了MwNTs/CdS复合材料,并用TEM、XRD、FT-IR及UV-vis等技术对材料的结构、形貌和性质进行表征.研究结果表明:硫化镉纳米粒子附着在多壁碳纳米管表面,且无团聚现象.     

Copper-mediated synthesis of PdI_2 colloidal spheres

A novel copper-mediated solvothermal method was proposed for synthesizing colloidal spheres of a new composition,palladium iodide(PdI2).Typical procedure was designed to involve the introduction of cupric chloride(CuCl2) as weak oxidant.CuCl2 was found to be essential for preventing the easy formation of palladium deposits as well as facilitating the synthesis and assembly.Under the co-effect of CuCl2 and the surfactant of polyvinylpyrrolidone(PVP),neutral PdI2 colloidal spheres with narrow size distributio...     

Video-tape observation of the crystal growth and morphology of colloidal single crystals

Crystal growth and morphology of colloidal crystals of silica spheres (81.2 nm in diameter) are observed directly on a video-tape camera. Crystal growth from the round-shaped, small single crystals to the angular-shaped ones is clear. It is observable that the single crystals are packed densely and separated from each other with the grain boundaries. The morphology of colloidal crystals is quite similar to that of typical crystals such as metals, proteins, and ice.     

Colloidal crystals of cationic spheres

Colloidal single crystals of cationic polymer spheres (198–250 nm in diameter) in deionized aqueous dispersions were formed for the first time. The spheres used were poly(styrene-co-methacryloyloxyphenyldimethylsulfonium) cations. These cations are unstable in deionized suspensions with mixed beds of cation-exchange and anion-exchange resins. This was clarified by reflection spectroscopy, pH, conductance and -potential measurements for 250 days after suspension preparation. Colloidal crystals formed over a period of 24 h for the deionized suspensions at sphere concentrations higher than 0.09 in volume fraction. The nearest-neighbor intersphere distances coincide satisfactorily with the calculated values using the diameter and the concentration of the spheres. Alloy crystals formed from binary mixtures of the cationic polymer spheres and the anionic silica spheres when the ratio of the volume fraction of cationic spheres against the sum of the both cationic and anionic spheres was smaller than 0.3.     

Facile synthesis and characterization of monocrystalline cubic ZrO2 nanoparticles

Crystalline ZrO₂ nanoparticles were prepared from zirconium isopropoxide by slow hydrolysis and subsequent hydrothermal treatment of solutions containing various amounts of sodium hydroxide at 180 °C. Whereas moderately basic solutions lead to the formation of nanoparticles of monoclinic ZrO₂ with plate-like morphology, and nanoparticles of the cubic ZrO₂ high-temperature polymorph with diameters of approx. 5 nm were obtained from strongly basic solutions. The morphology, structure and properties of as-synthesized nanoparticles were characterized using HRTEM, XRD, Raman spectroscopy, UV–vis, PL spectroscopy and BET measurements. The formation of both, the monoclinic and the cubic polymorph, was confirmed by electron microscopy and Raman spectroscopy. The crystallinity and morphology of the resulting ZrO₂ nanoparticles can be adjusted by the choice of the reaction conditions. The cubic ZrO₂ nanoparticles have a high surface area (300 m²/g) and exhibit a strong photoluminescence in the UV region.     

Fabrication of functional hollow carbon spheres with large hollow interior as active colloidal catalysts

In this study,we have established a facile method to synthesize functional hollow carbon spheres with large hollow interior,which can act as active colloidal catalysts.The method includes the following steps:first,hollow polymer spheres with large hollow interior were prepared using sodium oleate as the hollow core generator,and 2,4-dihydroxybenzoic acid and hexamethylene tetramine(HMT) as the polymer precursors under hydrothermal conditions;Fe 3+ or Ag + cations were then introduced into the as-prepared hollow polymer spheres through the carboxyl groups;finally,the hollow polymer spheres can be pseudomorphically converted to hollow carbon spheres during pyrolysis process,meanwhile iron or silver nanoparticles can also be formed in the carbon shell simultaneously.The structures of the obtained functional hollow carbon spheres were characterized by TEM,XRD,and TG.As an example,Ag-doped hollow carbon spheres were used as colloid catalysts which showed high catalytic activity in 4-nitrophenol reduction reaction.     

Controlled synthesis, growth mechanism, and properties of monodisperse CdS colloidal spheres

Highly monodisperse submicrometer CdS colloidal spheres (CSCS) with a controllable and tunable size (between 80 and 500 nm) have been synthesized through a facile solvothermal technique. Owing to the controllability of the reaction process, the growth mechanism of the colloidal spheres has been elucidated in detail. The whole growth process can be summarized as homogenous and slow nucleation of nanocrystals, formation of "cores" through 3D-oriented attachment of nanocrystals, and further surface-induced growth to monodisperse colloidal spheres through in situ formation and random attachment of additional nanocrystals. It has been demonstrated that the obtained CSCS colloidal particles are able to be assembled into films which show characteristic stop band gaps of photonic crystals. By using the CSCS as a template, Ag2S, Bi2S3, Cu2S, HgS, and Sb2S3 colloidal spheres, which are difficult to obtain directly, have also been prepared successfully through ion exchange.