Control for oriented growth of large size KCl crystals by the competition between spontaneous and induced nucleation/growth on a Langmuir-Blodgett film

Langmuir-Blodgett (LB) film of stearic acid was used as template to induce the nucleation and growth of KCl crystals when the KCl solution was cooled from 50 to 25 degrees C. When the LB film template was vertically dipped into the solution, only induced crystals with (1 1 0) orientation were formed. However, if the template was horizontally placed into solutions, both the induced nuclei at the solution/film interface and spontaneous nuclei formed in solution were simultaneously absorbed onto the LB film, and then grew further to form crystals. X-ray diffraction (XRD) patterns and optical microscopy images showed that the orientation and morphology of the crystals were controlled properly by changing the orientation and position of the LB films in the solutions.

Phosphine-Free Synthesis of High-Quality CdSe Nanocrystals in Noncoordination Solvents: "Activating Agent" and "Nucleating Agent" Controlled Nucleation and Growth

CdSe nanocrystals (NCs) are prepared in noncoordination solvents (1-octadecene (ODE) and paraffin liquid) with Ion g-chain primary alkylamine as the sole ligand, ODE-Se, and cadmium fatty acid salt as precursors. The obtained NCs meet the four fundamental parameters for high-quality NCs: high crystallinity, narrow size distribution, moderate photoluminescence quantum yield, and broad range size tunableness. Further, by simply regulating the relative molar ratio of alkylamine to cadmium precursor, the regular sized "nuclei" and final obtained NCs can be produced predictably within a certain size range.

Controlled synthesis of monodisperse nanocrystals by a two-phase approach without the separation of nucleation and growth processes

The synthesis of monodisperse nanocrystals is an important topic in the field of nanomaterials not only for practical applications, but also for scientific interest in fundamental research. In this feature article, we mainly focus on synthesis of monodisperse nanocrystals by a two-phase approach without the separation of nucleation and growth processes, and report some progress made recently in the observation and understanding of nucleation and growth of semiconductor nanocrystals. Firstly, a novel two-phase approach to monodisperse nanocrystals, which is different from the well-established synthesis models, is discussed. We demonstrate that the two-phase approach has a quite lengthy nucleation process, and can be applied to the synthesis of many kinds of binary monodisperse nanocrystals.

Nucleation in A/B/AB blends: Interplay between microphase assembly and macrophase separation

We study the interplay between microphase assembly and macrophase separation in A/B/AB ternary polymer blends by examining the free energy of localized fluctuation structures (micelles or droplets), with emphasis on the thermodynamic relationship between swollen micelles (microemulsion) and the macrophase-separated state, using self-consistent field theory and an extended capillary model. Upon introducing homopolymer B into a micelle-forming binary polymer blend A/AB, micelles can be swollen by B. A small amount of component B (below the A-rich binodal of macrophase coexistence) will not affect the stability of the swollen micelles. A large excess of homopolymer, B, will induce a microemulsion failure and lead to a macrophase separation.

Carbon dioxide pressure induced heterogeneous and homogeneous Heck and Sonogashira coupling reactions using fluorinated palladium complex catalysts

The Heck reaction of iodobenzene and methyl acrylate was investigated with CO2-philic Pd complex catalysts having fluorous ponytails and the organic base triethylamine (Et3N) in the presence of CO2 under solventless conditions at 80 degrees C. The catalysts are not soluble in the organic phase in the absence Of CO2 and the reaction occurs in a solid-liquid biphasic system. When the organic liquid mixture is pressurized by CO2, CO2 is dissolved into the organic phase and this promotes the dissolution of the I'd complex catalysts. As a result, the Heck reaction occurs homogeneously in the organic phase, which enhances the rate of reaction. This positive effect Of CO2 pressurization competes with the negative effect that the reacting species are diluted by an increasing amount of CO2 molecules dissolved. Thus, the maximum conversion appears at a CO2 pressure of around 4 MPa under the present reaction conditions. The catalysts are separated in the solid granules by depressurization and are recyclable without loss of activity after washing with n-hexane and/or water.

Nucleation and growth of glycine crystals with controllable sizes and polymorphs on Langmuir-Blodgett films

Control of crystal polymorph and size is very important in many application fields. Herein we demonstrate that Langmuir-Blodgett (LB) films of stearic acid (SA) and octadecylamine (ODA) can serve as templates and generate different polymorphs of glycine crystals. In the neutral aqueous solutions, gamma-glycine crystallizes on LB films of ODA while the polymorphic outcome becomes the (x-form on LB films of SA. These observed results could be explained by the electrostatic interactions and geometric lattice matching at the LB film/crystal interfaces, respectively. By keeping the appropriate supersaturation, we have successfully controlled the number of crystals grown on LB films; for example, in some certain cases, only one piece of crystal was grown on LB films in solution. Therefore, large crystals of centimeter size could be prepared. These experimental results suggest a new approach to produce an organic crystal with bulk scale.

(R,R)-DPEN-modified Ru/gamma-Al2O3 - An efficient heterogeneous catalyst for enantioselective hydrogenation of acetophenone

An efficient enantioselective catalyst of 5 wt.% Ru/-gamma-Al2O3 modified with R,R-1,2-diphenylethylene-diamine ((R,R)-DPEN) for the hydrogenation of a non-activated aromatic ketone of acetophenone has been investigated, a relatively high enantiomeric excess (ee) of 60.5% was obtained at both the conversion and selectivity larger than 99%, it was about three times higher than the ee values reported up to now for acetophenone hydrogenation with the supported transition metal catalysts modified by chiral reagents. The influences of some reaction parameters such as phosphine ligand, substrate/catalyst/modifier molar ratios, base, solvent, pressure and reaction temperature have been discussed. The chiral modifier of (R,R)-DPEN was very important in controlling the enantioselectivity through adsorption competing with other substrates on the surface of active metal species. The phosphine ligand and base were also important and indispensable in the present reaction.

Isothermal crystallization kinetics of iPP during self-nucleation process

In this paper, the isothermal crystallization kinetics of polypropylene (iPP) during self-nucleation was studied by means of differential scanning calorimetry(DSC). The iPP was melted at 438 K and then isothermally crystallized in the range of temperature between 421 and 425 K. The mechanism of nucleation and growth of iPP was discussed. The Avrami equation was applied to analyzing the process of isothermal crystallization of iPP from the melt. The average value of Avrami exponent is n=3.01, suggesting that the primary crystallization maybe corresponds to three-dimensional spherulitic growth. The K-g value obtained from Lauritzen-Hoffman equation is 1.128 X 10(5) K-2, which suggests that crystallization species should be regime I. The decrease of crystallization active energy and chain folding work indicates that the self-nucleation can greatly promote the overall crystallization of iPP.

Hole nucleation and growth induced by crystallization and microphase separation of thin semicrystalline diblock copolymer films

We have investigated the hole nucleation and growth induced by crystallization of thin crystalline-coil diblock copolymer films. Semicrystalline rodlike assemblies from neutral/selective binary solvent are used as seeds to nucleate crystallization at temperatures above the glass transition temperature (T-g) but below melting point (T-m). The crystallization of nanorods drives neighboring copolymer chains to diffuse into the growing nanorods. Depletion of copolymer chains yields hole nucleation and growth at the edge of the nanorods. Simultaneously, the polymer chains unassociated into the nanorods were oriented by induction from the free surface and the substrate, leading to limitation of the hole depth to the lamellar spacing, similar to20 nm. The holes, as well as the nanorods, grow as t(alpha), where t is the annealing time and a crossover in the exponent a. is found. The orientation and stretching of the copolymer chains by the surface and interface are believed to accelerate the crystallization, and in turn, the latter accelerates the growth rate of the holes. At T > T-m, the grains melt and the copolymer chains relax and flow into the first layer of the film.

Molecular weight effects on the phase morphology of PS/P4VP blend films on homogeneous SAM and heterogeneous SAM/Au substrates

The effects of the molecular weight of polystyrene (PS) component on the phase separation of PS/poly(4-vinylpyridine) (PS/P4VP) blend films on homogeneous alkanethiol self-assembled monolayer (SAM) and heterogeneous SAM/Au substrates have been investigated by means of atomic force microscopy (AFM). For the PS (22.4k)/P4VP (60k) system, owing to the molecular weight of PS component is relatively small, the well-aligned PS and P4VP stripes with good thermal stability are directed by the patterned SAM/Au surfaces. With the increase of the molecular weight of PS component (for the PS (582k)/P4VP (60k) system), the diffusion of P4VP is hindered by the high viscosity of PS during the fast spin-coating process. The phase separation behavior of PS/P4VP on the SAM/Au patterned substrates is similar to that on the homoueneous SAM and cannot be easily directed by the patterned SAM surfaces even though the characteristic length of the lateral domain morphology is commensurate with the stripe width.

Use of atomic force microscopy for imaging the initial stage of the nucleation of calcium phosphate in Langmuir-Blodgett films of stearic acid

The nucleation of calcium phosphate on the substrate of steatic acid Langmuir-blodgett film at the initial stage was investigated by atomic force microscopy. Nano-dots, nano-wires and nano-islands were observed in sequence for the first time, reflecting the nucleation of calcium phosphate and the molecular arrangement of carboxylic layer. The nucleation rates perpendicular and parallel to the carboxylic terminal group were estimated from the height and diameter of the calcium phosphate crystals, respectively. And this stage was distinct from the late explosive grown stage, in which the change of the morphology was not obvious. The approaches based on this discovery would lead to the development of new strategies in the controlled synthesis of inorganic nano-phases and the assembly of organized composite and ceramic materials.

A nonmonotonic dependence of standard rate constant on reorganization energy for heterogeneous electron transfer processes on electrode surface

In the present work a nonmonotonic dependence of standard rate constant (k(0)) on reorganization energy (lambda) was discovered qualitatively from electron transfer (Marcus-Hush-Levich) theory for heterogeneous electron transfer processes on electrode surface. It was found that the nonmonotonic dependence of k(0) on lambda is another result, besides the disappearance of the famous Marcus inverted region, coming from the continuum of electronic states in electrode: with the increase of lambda, the states for both Process I and Process II ET processes all vary from nonadiabatic to adiabatic state continuously, and the lambda dependence of k(0) for Process I is monotonic thoroughly, while for Process II on electrode surface the lambda dependence of k(0) could show a nonmonotonicity.

Cyclic voltammetry for predicting oxidation process in heterogeneous catalysis

Catalytic reactions with different oxidation process were investigated and correlated to the electrochemical properties of the catalysts. The activity of suprafacial reaction is closely related to the area of redox peak, while that of the intrafacial one is to the match of redox potentials. Accordingly, it is supposed that cyclic voltammetry (CV) measurement could be a means for predicting the oxidation process in heterogeneous catalysis.

Effects of solution viscosity on heterogeneous electron transfer across a liquid/liquid interface

Scanning electrochemical microscopy (SECM) is employed to investigate the effect of solution viscosity on the rate constants of electron transfer (ET) reaction between potassium ferricyanide in water and 7,7,8,8-tetracyanoquinodimethane (TCNQ) in 1,2-dichloroethane. Either tetrabutylammonium (TBA(+)) or ClO4- is chosen as the common ion in both phases to control the interfacial potential drop. The rate constant of heterogeneous ET reaction between TCNQ and ferrocyanide produced in-situ, k(12), is evaluated by SECM and is inversely proportional to the viscosity of the aqueous solution and directly proportional to the diffusion coefficient of K4Fe(CN)(6) in water when the concentration of TCNQ in the DCE phase is in excess. The k(12) dependence on viscosity is explained in terms of the longitudinal relaxation time of the solution. The rate constant of the heterogeneous ET reaction between TCNQ and ferricyanide, k(21), is also obtained by SECM and these results cannot be explained by the same manner.