The dominant role of the solvent-water interface in water droplet templating of polymers

We investigate the formation of microstructured polymer networks known as Breath Figure templated structures created by the presence of water vapour over evaporating polymer solutions. We use a highly controlled experimental approach to examine this dynamic and non-equilibrium process to uniquely compare pure solvent systems with polymer solutions and demonstrate using a combination of optical microscopy, focused ion-beam milling and SEM analysis that the porous polymer microstructure is completely controlled by the interfacial forces that exist between the water droplet and the solvent until a final drying dilation of the imprints. Water droplet contact angles are the same in the presence or absence of polymer and are independent of size for droplets above 5 μm. The polymer acts a spectator that serves to trap water droplets present at the air interface, and to transfer their shape into the polymer film. For the smallest pores, however, there are unexpected variations in the contact angle with pore size that are consistent with a possible contribution from line tension at these smaller dimensions. © The Royal Society of Chemistry.

CO2-gasification of a lignite coal in the presence of an iron-based oxygen carrier for chemical-looping combustion

Chemical-looping combustion (CLC) has the inherent property of separating the product CO2 from flue gases. Instead of air, it uses an oxygen carrier, usually in the form of a metal oxide, to provide oxygen for combustion. All techniques so far proposed for chemical looping with solid fuels involve initially the gasification of the solid fuel in order for the gaseous products to react with the oxygen carrier. Here, the rates of gasification of coal were compared when gasification was undertaken in a fluidised bed of either (i) an active Fe-based oxygen carrier used for chemical looping or (ii) inert sand. This enabled an examination of the ability of chemical looping materials to enhance the rate of gasification of solid fuels. Batch gasification and chemical-looping combustion experiments with a German lignite and its char are reported, using an electrically-heated fluidised bed reactor at temperatures from 1073 to 1223 K. The fluidising gas was CO2 in nitrogen. The kinetics of the gasification were found to be significantly faster in the presence of the oxygen carrier, especially at temperatures above 1123 K. A numerical model was developed to account for external and internal mass transfer and for the effect of the looping agent. The model also included the effects of the evolution of the pore structure at different conversions. The presence of Fe2O3 led to an increase in the rate of gasification because of the rapid oxidation of CO by the oxygen carrier to CO2. This resulted in the removal of CO and maintained a higher mole fraction of CO2 in the mixture of gas around the particle of char, i.e. within the mass transfer boundary layer surrounding the particle. This effect was most prominent at about 20% conversion when (i) the surface area for reaction was at its maximum and (ii) because of the accompanying increase in porosity and pore size, intraparticle resistance to gas mass transfer within the particle of char had fallen, compared with that in the initial particle. Excellent agreement was observed between the rates predicted by the numerical model and those observed experimentally. ©2013 Elsevier Ltd. All rights reserved.

Preparation and AFM characterization of self-ordered porous alumina films on semi-insulated gaas substrate

Self-ordered porous alumina films on a semi-insulated GaAs substrate were prepared in oxalic acid aqueous solutions by three-step anodization. The I-t curve of anodization process was recorded to observe time effects of anodization. Atomic force microscopy was used to investigate structure and morphology of alumina films. It was revealed that the case of oxalic acid resulted in a self-ordered porous structure, with the pore diameters of 60-70 nm, the pore density of the order of about 10(10) pore cm(-2), and interpore distances of 95-100nm. At the same time the pore size and shape change with the pore widening time. Field-enhanced dissolution model and theory of deformation relaxation combined were brought forward to be the cause of self-ordered pore structure according to I-t curve of anodization and structure characteristics of porous alumina films. (c) 2006 Elsevier Ltd. All rights reserved.

Porous ZnAl2O4 spinel nanorods doped with Eu3+: synthesis and photoluminescence

Eu3+-doped zinc aluminate (ZnAl2O4) nanorods with a spinel structure were successfully synthesized via an annealing transformation of layered precursors obtained by a homogeneous coprecipitation method combined with surfactant assembly. These spinel nanorods, which consist of much finer nanofibres together with large quantities of irregular mesopores and which possess a large surface area of 93.2 m(2) g(-1) and a relatively narrow pore size distribution in the range of 6 - 20 nm, are an ideal optical host for Eu3+ luminescent centres. In this nanostructure, rather disordered surroundings induce the typical electric-dipole emission (D-5(0) --> F-7(2)) of Eu3+ to predominate and broaden.

Preparation and AFM characterization of self-ordered porous alumina films on semi-insulated gaas substrate

Self-ordered porous alumina films on a semi-insulated GaAs substrate were prepared in oxalic acid aqueous solutions by three-step anodization. The I-t curve of anodization process was recorded to observe time effects of anodization. Atomic force microscopy was used to investigate structure and morphology of alumina films. It was revealed that the case of oxalic acid resulted in a self-ordered porous structure, with the pore diameters of 60-70 nm, the pore density of the order of about 10(10) pore cm(-2), and interpore distances of 95-100nm. At the same time the pore size and shape change with the pore widening time. Field-enhanced dissolution model and theory of deformation relaxation combined were brought forward to be the cause of self-ordered pore structure according to I-t curve of anodization and structure characteristics of porous alumina films. (c) 2006 Elsevier Ltd. All rights reserved.

Template-assisted syntheses of two novel porous zirconium methylphosphonates

Two porous zirconium methylphosphonates (designated as ZMPmi and ZMPme respectively) were synthesized by using dibutyl methylphosphonate (DBMP) as a template. Two efficient post-synthetic treatments were developed to remove the incorporated template without destroying the hybrid structures. The materials were characterized by SEM, EPMA, TG, DTA, FTIR, and NMR. Specific surface area and porosity were evaluated by BET, alpha(s)-plots and DFT methods based on N-2 adsorption-desorption isotherms. The specific surface areas of ZMPmi and ZMPme are determined to be 279 and 403 m(2) g(-1) and the maxima of pore size distributions are at 0.7 and 1.3 nm respectively. (c) 2005 Elsevier Inc. All rights reserved.

Effect of drying methods on the structure and catalytic combustion activity of Mn-substituted hexaaluminate catalysts

Conventional oven drying (COD) and supercritical drying (SCD) methods were applied to the preparation of Mn-substituted hexaaluminate (BaMnA(11)O(19-alpha)) catalysts. The effect of drying methods on phase composition, specific surface area, pore structure and combustion activity of the samples was investigated. The samples obtained by SCD have higher surface area, narrower pore size distribution, and higher combustion activity than those obtained by COD.

Fischer-Tropsch reaction over cobalt catalysts supported on zirconia-modified activated carbon

An attractive Fischer-Tropsch catalyst was prepared using an activated carbon as carrier to support cobalt based catalysts. Zr promoted Co/AC catalysts remarkably enhanced the activity and the selectivity toward diesel distillates and lower the methane selectivity. This modification may be attributed to specific behavior of activated carbon with high surface area and the weak interaction between metallic cobalt active sites and activated carbon. It was emphasized that the pore size of activated carbon played a very important role in restricting the growth of carbon chain to wax.

Short columns with molecularly imprinted monolithic stationary phases for rapid separation of diastereomers and enantiomers

Three molecularly imprinted monolithic columns with different length but almost identical column volume had been prepared. It was observed that the separation factors of diastereomers and enantiomers were almost unaffected by column length. However, the short column with dimension of 38 mm x 8 mm W. showed much lower resistance to flow rate so that it could be operated at much higher flow rates. By combining stepwise gradient elution with elevated flow rate, the diastereomers of cinchonine and cinchonidine and the enantiomers of Cbz-DL-Trp and Fmoc-DL-Trp were successfully separated within 3 min on the short column with dimension of 38 mm. x 8 mm i.d.. Based on the above results, a cinchonine imprinted monolithic disk with dimension of 10 mm x 16 mm W. was further developed. The SEM image and the pore size distribution profile showed that large flow-through pores are present on the prepared monolith, which allowed mobile phase to flow through the disk with very low resistance. Chromatographic performances on the monolithic disk were almost unchanged compared with the long columns. A rapid separation of cinchonine and cinchonidine was achieved in 2.5 min at the flow rate of 9.0 ml/min. Furthermore, it was observed that there was almost no effect of the flow rate on the dynamic binding capacity at high flow rates. In addition, the effect of the loading concentration of analytes on the dynamic binding capacity, namely adsorption isotherm, was also investigated. A non-linear adsorption isotherm of cinchonine was observed on the molecularly imprinted monolith with cinchonine as template, which might be a main reason to result in the peak tailing of template molecule. (C) 2004 Elsevier B.V. All rights reserved.

Chiral synthesis on catalysts immobilized in microporous and mesoporous materials

This paper reviews the recent progress made in the asymmetric synthesis on chiral catalysts in porous materials and discusses the effects of surface and pores on enantio-selectivity (confinement effect). This paper also summarizes various approaches of immobilization of the chiral catalysts onto surfaces and into pores of solid inorganic supports such as microporous and mesoporous materials. The most important reactions surveyed for the chiral synthesis in porous materials include epoxidation. hydrogenation, hydroformylation, Aldol and Diels-Alder reactions, etc. The confinement effect originated from the surfaces and the pores turns out to be a general phenomenon. which may make the enantioselectivity increase (positive effect) or decrease (negative effect). The confinement effect becomes more pronounced particularly when the bonding between the catalyst and the surface is more rigid and the pore size is tuned to a suitable range. It is proposed that the confinement in chiral synthesis is essentially a consequence of subtle change in transition states induced by weak-interaction in pores or on surfaces. It is also anticipated that the enantioselectivity could be improved by tuning the confinement effect based on the molecular designing of the pore/surface and the immobilized catalysts according to the requirements of chiral reactions.