Room temperature synthesis of HgTe nanocrystals

We report a new method to synthesize monodisperse zinc blende HgTe nanocrystals at room temperature in noncoordinating solvent-octadecene. Thiol was needed to control the reaction at a suitable nucleation and growth speed. In the early stage of the reaction, HgTe nanocrystals formed aggregates, and then the aggregates were dispersed and individual dot-shaped nanocrystals were formed with stronger photoluminescence emitting. UV-vis, photoluminescence, and TEM have been used to study the properties of as-prepared HgTe nanocrystals.     

Room temperature synthesis of upconversion fluorescent nanocrystals

Synthesis of nanocrystals that exhibit strong upconversion (UC) luminescence upon infrared excitation has been challenging due to the stringent control needed over experimental variables. Herein, we report a method to synthesize nanocrystals demonstrating high UC at room temperature in aqueous solution on graphene.     

Low temperature induced synthesis of TiN nanocrystals

TiN nanocrystals were successfully prepared through the direct reaction between TiCl(4) and NaNH(2) induced at 300 degrees C. The yield based on Ti is approximately 80%. X-ray powder diffraction indicated that the product was cubic TiN with a lattice constant of a = 4.243 A. Transmission electron microscopy revealed that nanocrystalline TiN with a diameter of 10 nm or so and extremely long straight rods were synthesized. The possible formation mechanism was also proposed.     

Altering the crystal morphology of silicalite-1 through microemulsion-based synthesis

The crystal morphology of silicalite-1 was adjusted through a microemulsion-based hydrothermal synthesis. The surfactant cetyltrimethylammonium bromide (CTAB) with cosurfactant butanol was used to form water-in-oil microemulsions containing the silicalite-1 synthesis gel. The crystal morphology of silicalite-1 was adjusted from coffin-shaped to novel rod-shaped and to irregular-shaped nanoparticles by varying the microemulsion composition. Silicalite-1 synthesized in the microemulsion has a smaller size and a more narrow size distribution than that produced by conventional synthesis without the microemulsion. The novel morphology of silicalite-1 may facilitate assembly into films and find applications in separation and catalysis.     

Reverse microemulsion-mediated synthesis of silica-coated gold and silver nanoparticles

A reverse microemulsion method is reported for preparing monodispersed silica-coated gold (or silver) nanoparticles without the use of a silane coupling agent or polymer as the surface primer. This method enables a fine control of the silica shell thickness with nanometer precision. As compared to the St?ber method reported for direct silica coating, which can only coat large gold particles ( approximately 50 nm in diameter) at low concentrations (<1.5 x 10(10) particles/mL), this new approach is capable of coating gold particles of a wide range of sizes (from 10 to 50 nm) at a much higher concentration ( approximately 1.5 x 10(13) particles/mL). Moreover, it enables straightforward surface functionalization via co-condensation between tetraethyl orthosilicate and another silane with the desired functional groups. The functional groups introduced by this method are readily accessible and thus useful for various applications.     

Novel method for synthesis of titanium silicalite-1 (TS-1)

Titanium silicalite-1 (TS-1) was easily synthesized using inorganic silicon and titanium source, tetrapropylammonium bromide (TPABr) or TPAOH as templating molecule, NH3· H2O, HDA or TEAOH etc. as base sources. In this system, TPA cations (come from TPABr or TPAOH) served as tern-plating agents to direct the MFI structure. NH3H2O, TEAOH or HDA etc. provides the alkalinity necessary for crystallization. X-ray diffraction, UV-Vis, ER spectroscopies, SEM, 29 Si MAS NMR showed that the zeolites obtained possessed all the structural characteristics of TS-1, and titanium atoms were introduced into the framework in TS-1. This material was proved to have high crystallinity and high catalytic activity to allyl chloride epoxidation and propylene epoxidation. All the samples synthesized had similar catalytic properties with a standard TS-1 through compared inorganic reactant system with organic synthesis system using propylene epoxidation. The effects of silicon source and TPABr/SiO2 ratio were discussed.     

Extensions in the synthesis and catalytic application of titanium silicalite-1

Titanium silicalite-1 (TS-1) was prepared by microwave heating of a SiO₂–TiO₂ xerogel, which was dry-impregnated with tetrapropylammonium hydroxide (TPAOH). Highly crystalline product was obtained, with the yields higher than 90%, within 30 min after microwave irradiation. These are significant advantages over the conventional oven heating using alkoxide precursors in liquid phase, which requires 1-2 day crystallization time with low product yields. Sub-micron sized SiO₂–TiO₂ prepared by thermal plasma process and Ti-containing mesoporous silica, Ti-HMS, were also tested as the solid phase precursor for TS-1. These were found inferior as precursor due to difficulties in uniformly wetting the surface with TPAOH. It was possible to prepare TS-1 using diethoxysiloxane-ethyltitanate (DESET, 93.75 mol Si:6.25 mol Ti) as a single mixed alkoxide precursor, but titanium species in the sample were highly unstable and large fraction of them came out from the framework to form TiO₂ clusters upon calcination. In addition, TS-1 monolith was prepared utilizing polyurethane foam as an infiltration medium of the synthesis gel. The prepared TS-1 monolith exhibited properties similar to those of TS-1 powders, but the elementary unit of the former was made of 1–2 micron-sized hexagonal shaped crystals, causing diffusion problems. Catalytic activities of all the prepared catalysts were evaluated using 1-hexene epoxidation as a probe reaction, and 2,5-dihydrofuran epoxidation was also examined using TS-1 as an alternative process to make 3,4-epoxytetrahydrofuran.     

Molecular hydrogen-induced nucleation of hydrogenated silicon nanocrystals at low temperature

Highly crystallized hydrogenated silicon layers were obtained via the treatment of hydrogenated polymorphous silicon films in a molecular hydrogen ambient. This contrasts other postdeposition studies that obtained nanocrystalline silicon films but necessitated either a plasma activation or high-temperature annealing. The structure of the samples was analyzed by Raman spectroscopy to determine the crystallite volume fraction, which was found to increase up to 80% within 1 hour of treatment. Atomic force microscopy (AFM) showed that the roughness of the surfaces was found to increase after the H₂ treatment. Optical transmission and spectroscopic ellipsometry revealed the pronounced porosity of the films characterized by a static refractive index that is below three, which is a low value for hydrogenated silicon films and a void fraction that is around 15% in the bulk of the films. The effect of the hydrogen molecules on the structure of the films was discussed in terms of the compressive stress exerted by the molecules, trapped in structural inhomogeneities, on the amorphous tissue. It is suggested that for this process to take effect, the films need to be porous and that the amorphous network needs to be in a “relaxed” state.     

Facile thermolysis synthesis of CuInS2 nanocrystals with tunable anisotropic shape and structure

Monodisperse CuInS(2) nanocrystals are produced by injecting mixed metal-oleate precursors into hot organic solvents containing the dissolved sulphur sources. A better understanding of the formation mechanism of CuInS(2) has enabled us to tailor anisotropic shapes in the form of triangular-pyramid, circular cone, and bullet-like rods with tunable crystal phases by varying the synthetic conditions.     

Influence of synthesis and operating parameters on silicalite-1 membrane properties

The present study deals with the synthesis of nanostructured silicalite-1 membranes on porous α-Al₂O₃ supports by a hydrothermal method. Different parameters including the synthesis conditions (temperature and alkalinity) and operating conditions (temperature and pressure) were investigated. The membranes were characterized by X-ray diffraction and scanning electron microscopy techniques. The optimum synthesis temperature and alkalinity were determined to be 160 °C and pH = 11, respectively. The permeability of CO₂ and CH₄ through the optimized membrane was determined by the pressure drop method. The results revealed that the main effective separation mechanism was adsorption. The permeation of CO₂ and CH₄ declined with increasing temperature, whereas high feed pressures enhanced the single gas flux. The CO₂ and CH₄ permeability values at 30 °C and 2 bar were 1.62 × 10^?7 and 2.07 × 10^?7 mol m^?2 s^?1 Pa^?1, respectively. Furthermore, the response surface methodology analysis confirmed the significance of all the variables and the proposed model. Excellent correlation between the experimental and predicted data (R² = 0.99) was obtained, confirming that response surface methodology is a powerful tool for modeling nanostructured silicalite-1 membrane processes.     

Room temperature solution synthesis of alkyl-capped tetrahedral shaped silicon nanocrystals

We report the room temperature solution synthesis of alkyl protected silicon nanocrystals. The nanocrystals are of unusually uniform tetrahedral morphology and of a limited size distribution. The nanocrystals were characterized by transmission and scanning electron microscopy as well as atomic force microscopy.     

Aggregative growth of silicalite-1

Precursor silica nanoparticles can evolve to silicalite-1 crystals under hydrothermal conditions in the presence of tetrapropylammonium (TPA) cations. It has been proposed that in relatively dilute sols of silica, TPA, water, and ethanol, silicalite-1 growth is preceded by precursor nanoparticle evolution and then occurs by oriented aggregation. Here, we present a study of silicalite-1 crystallization in more concentrated mixtures and propose that growth follows a path similar to that taken in the dilute system. Small-angle X-ray scattering (SAXS), cryogenic transmission electron microscopy (cryo-TEM), and high-resolution transmission electron microscopy (HRTEM) were used to measure nanoparticle size and to monitor zeolite nucleation and early-stage crystal development. The precursor silica nanoparticles, present in the clear sols prior to crystal formation, were characterized using two SAXS instruments, and the influence of interparticle interactions is discussed. In addition, SAXS was used to detect the onset of secondary particle formation, and HRTEM was used to characterize their structure and morphology. Cryo-TEM allowed for in situ visual observation of the nanoparticle population. Combined results are consistent with growth by aggregation of silica nanoparticles and of the larger secondary crystallites. Finally, a unique intergrowth structure that was formed during the more advanced growth stages is reported, lending additional support for the proposal of aggregative growth.     

First synthesis of silicalite-1 from a dry powder system via solid-solid transformation

Silicalite-1 has first been synthesized from a dry powder system with an adsorbedstate template, and is presented as a convincing example for direct solid-solid transformation process.     

Microreactor with integrated temperature control for the synthesis of CdSe nanocrystals

The recent needs in the nanosciences field have promoted the interest towards the development of miniaturized and highly integrated devices able to improve and automate the current processes associated with efficient nanomaterials production. Herein, a green tape based microfluidic system to perform high temperature controlled synthetic reactions of nanocrystals is presented. The device, which integrates both the microfluidics and a thermally controlled platform, was applied to the automated and continuous synthesis of CdSe quantum dots. Since temperature can be accurately regulated as required, size-controlled and reproducible quantum dots could be obtained by regulating this parameter and the molar ratio of precursors. The obtained nanocrystals were characterized by UV-vis and fluorescence spectrophotometry. The band width of the emission peaks obtained indicates a narrow size distribution of the nanocrystals, which confirms the uniform temperature profile applied for each synthetic process, being the optimum temperature at 270 °C (full width at half maximum = 40 nm). This approach allows a temperature controlled, easy, low cost and automated method to produce quantum dots in organic media, enhancing its application from laboratory-scale to pilot-line scale processes.     

Adsorption of lipids on silicalite-1

Russian Journal of Physical Chemistry A - The adsorption of egg lecithin and cholesterol from chloroform solutions onto silicalite-1 (hydrophobic silica with MFI zeolite structure) is investigated....     

Localized surface plasmon resonances of anisotropic semiconductor nanocrystals

We demonstrate that anisotropic semiconductor nanocrystals display localized surface plasmon resonances that are dependent on the nanocrystal shape and cover a broad spectral region in the near-IR wavelengths. In-plane and out-of-plane dipolar resonances were observed for colloidal dispersions of Cu(2-x)S nanodisks, and the wavelengths of these resonances are in good agreement with calculations carried out in the electrostatic limit. The wavelength, line shape, and relative intensities of these plasmon bands can be tuned during the synthetic process by controlling the geometric aspect ratio of the disk or using a postsynthetic thermal-processing step to increase the free carrier densities.     

Sorption of alkanediols by silicalite-1

Isotherms for the sorption of linear alkanediols HO(CH₂) _n OH (n = 2, 4, 6, 8) from aqueous solution by silicalite-1 at 25° are reported.     

桥联有机硅烷组装多级孔TS-1聚集体及其催化性能研究（英文）

TS-1分子筛在H_2O_2参与的有机物分子选择氧化及环氧化反应中具有优异的催化性能,一直广受关注.目前,随着精细化工反应中大分子及液相反应的增多,目前工业上使用的微米级尺寸的沸石晶粒催化材料因其狭窄的孔道和较大的扩散阻力而越来越不能满足工业的实际生产需求与应用.小晶粒纳米沸石由于具有较大的外比表面积和较高的晶内扩散速率,因而在提高催化剂的利用率、增强大分子转化能力、减小深度反应、提高选择性以及降低结焦失活等方面均表现出优越的性能.然而,尺寸低于100 nm的沸石又存在着分离问题.因此,具有高催化活性、又能一步实现分离与回收的纳米沸石聚集体的合成,引起了人们的研究兴趣.目前可以通过使用聚苯乙烯球,球型阴离子交换树脂,硅烷化聚合物,聚合诱导胶体聚集(PICA)等实现纳米沸石聚集体材料的合成.其中采用有机硅烷化试剂来制备多级孔纳米沸石聚集体材料提供了一种新的路线.在沸石晶体表面修饰上有机硅烷化试剂,含Si–C键的有机硅烷化物种可以有效地阻止沸石颗粒的晶体生长,抑制形成大的沸石晶体,从而得到纳米粒子聚集体;同时有机硅烷化物种也对纳米沸石进行了表面改性,提高了其疏水性.特别是在有机相中硅烷化沸石可以形成小的、均匀的、聚集的疏水性的纳米沸石.同时,硅烷化试剂的本质和分子大小是沸石聚集体中多级孔大小的决定性因素.具有可调结构的多级孔沸石晶体可以通过在常规的碱性沸石合成混合物溶液中添加一个两性有机硅表面活性剂而合成.研究发现,固定在沸石纳米晶表面的机硅烷物种Si–C键能部分抑制纳米颗粒进一步聚集成较大的晶体,使用硅烷化晶种的方法可以合成具有高比表面的多级孔ZSM-5等沸石.然而,目前已报道的通过硅烷化晶种方法中得到的多级孔TS-1沸石材料的尺寸仅有100–150 nm,仍不利于分离和回收.近来桥联有机硅烷试剂进入人们的视野——通过干胶法合成多级孔β沸石,然而它们的尺寸也只有300–500 nm,反应分离和回收仍然非常困难.本文采用有机桥联硅烷化合物作为硅烷化试剂,将TS-1纳米沸石晶种或者晶体组装聚集成大的沸石聚集体.TEM和SEM结果表明,桥联有机硅烷在沸石晶体的聚集和后续的晶体生长中起到了非常有效的作用,成功地将100 nm左右的纳米沸石晶种或晶体桥联/组装成宏观大尺寸(5–40μm)的沸石聚集体.这些TS-1聚集体具有较好的机械强度,即使连续超声1 h也不会毁坏其结构,表明所得到的沸石材料可以在制备上解决分离困难并且在催化应用上容易回收.XRD,BET以及UV-Vis分析结果表明,引入在TS-1沸石晶种或者晶体溶液中有机硅烷试剂不会影响沸石的晶体结构、微孔体积以及Ti的配位状态.将H_2O_2作为氧化剂评价TS-1沸石聚集体和传统的纳米TS-1在烯烃环氧化反应中的催化性能,结果表明,硅烷化步骤对小分子己烯氧化的活性和选择性的影响不大,在环己烯大分子的氧化反应里表现出了较高的活性和选择性.