Acid catalyzed synthesis of ordered bifunctionalized mesoporous organosilicas with large pore

Thiol-functionalized mesoporous ethane-silicas with large pore were synthesized by co-condensation of 1,2-bis(trimethoxy-sily)ethane (BTME) with 3-mercaptopropyltrimethoxysilane (MPTMS) using nonionic oligomeric polymer C1H (OCH(2)-CH(2))(10)OH (Brij-76) or poly(alkylene oxide) block copolymer (P123) as surfactant in acidic medium. The results of powder X-ray diffraction (XRD), nitrogen gas adsorption, and transmission electron microscopy (TEM) show that the resultant materials have well-ordered hexagonal mesoscopic structure with uniform pore size distributions. (29)Si MAS NNR, (13)C CP-MAS NMR. FT-IR, and UV Raman spectroscopies confirm the attachment of thiol functionalities in the mesoporous ethane-sificas. The maximum content of the attached thiol group (-SH) in the mesoporous framework is 2.48mmol/g. The ordered mesoporous materials are efficient Hg(2+) adsorbents with almost every -SH site accessible to Hg(2+). In the presence of various kinds of heavy metal ions such as Hg(2+), Cd(2+), Zn(2+), Cu(2+) and Cr(3+), the materials synthesized using poly(alkylene oxide) block cooollxmier (Pluronic 123) g(2+), as surfactant show almost similar affinity to Hg(2+), Cd(2+), and Cr(3+), while the materials synthesized using ofigomeric polymer C(18)H(37)(OCH(2)CH(2))(10)OH (Brij-76) as surfactant exhibit high selectivity to Hg(2+). (C) 2004 Elsevier Inc. All rights reserved.

Synthesis of zeolite NaA membranes with high permeance under microwave radiation on mesoporous-layer-modified macroporous substrates for gas separation

This article reported the NaA zeolite membranes with high permeance synthesized with microwave heating method under different conditions: (1) on a macroporous substrate in gel, (11) on a mesoporous/macroporous (top-mesoporous-layer-modified macroporous) substrate in gel, and (111) on a mesoporous/macroporous substrate in sol. In general, the H-2 permeance of the NaA membranes by microwave heating in gel was usually at the level of 10(-6) mol s(-1) m(-2) Pa-1, much higher than that by the conventional hydrothermal synthesis. At similar H-2/C3H8 permselectivity. On the substrate modified mesoporous top layer, the H-2 permeance of the NaA membranes by microwave heating in gel or sol was further enhanced, while maintaining comparable H-2/C3H8 permselectivity, due to the prevention of penetration of the reagent into the pores of the macroporous substrate. Meanwhile, the synthesis took less time in sol than in gel on the mesoporous/macroporous substrate. The NaA membranes synthesized in sol had larger permeance than those in gel and underwent transformation in shorter time. The permeation of C3H8 suggested that there existed unwanted intercrystalline pores or defects in the membranes. © 2005 Elsevier B.V. All rights reserved.

Highly ordered periodic mesoporous ethanesilica synthesized under neutral conditions

Highly ordered mesoporous ethanesilica (MES) with 2D hexagonal structure was synthesized from 1,2-bis(trimethoxysilyl) ethane under neutral conditions for the first time. Divalent salts, such as NiCl2, MgCl2, ZnCl2, ZnSO4 and Zn(NO3)(2), were used to help the formation of the ordered mesostructure. The MES samples were characterized by powder X-ray diffraction, nitrogen sorption, transmission electron microscopy, FT-IR, C-13 and Si-29 solid-state NMR and thermal gravimetric analysis. A phase transition from a disordered wormhole-like structure to an ordered P6mm structure was observed upon the addition of inorganic salts. The pore size of the MES decreases from 4.7 to 3.9 nm with increasing content of the inorganic salts. Fluoride was also found to be important for the formation of ordered MES under neutral conditions.

Direct synthesis of highly ordered Fe-SBA-15 mesoporous materials under weak acidic conditions

Iron-substituted SBA-15 (Fe-SBA-15) materials have been synthesized via a simple direct hydrothermal method under weak acidic conditions. The powder X-ray diffraction (XRD), NZ sorption and transmission electron microscopy (TEM) characterizations show that the resultant materials have well-ordered hexagonal meso-structures. The diffused reflectance UV-vis and UV resonance Raman spectroscopy characterizations show that most of the iron ions exist as isolated framework species for calcined materials when the Fe/Si molar ratios are below 0.01 in the gel. The presence of iron species also has significant salt effects that can greatly improve the ordering of the mesoporous structure. Different iron species including isolated framework iron species, extraframework iron clusters and iron oxides are formed selectively by adjusting the pH values of the synthesis solutions and Fe/Si molar ratios. (c) 2005 Elsevier Inc. All rights reserved.

Structural relation properties of hydrothermally stable functionalized mesoporous organosilicas and catalysis

The surfactant assistant syntheses of sulfonic acid functionalized periodic mesoporous organosilicas with large pores are reported. A one-step condensation of tetramethoxysilane (TMOS) with 1,2-bis(trimethoxysilyi)ethane (BTME) and 3-mercaptopropyltrimethoxysilane (MPTMS) in highly acidic medium was performed in the presence of triblock copolymer Pluronic P123 and inorganic salt as additive. During the condensation process, thiol (-SH) group was in situ oxidized to sulfonic acid (-SO3H) by hydrogen peroxide (30 wt % H2O2). X-ray diffraction studies along with nitrogen and water sorption analyses reveal the formation of stable, highly hydrophobic, and well-ordered hexagonal mesoscopic structures in a wide range of -CH2CH2-concentrations in the mesoporous framework. The resultant materials were also investigated by Si-29 MAS and C-13 CP MAS NMR, thermogravimetric analyses, UV-Raman spectroscopy, and FT-IR spectroscopy. The role of the bridged organic group on the hydrothermal stability of the mesoporous materials was established, which revealed an enhancement in hydrothermal stability of the materials with incorporation of the bridged organic groups in the network. The catalytic performance of -SO3H functionalized mesoporous materials was investigated in the esterification of ethanol with acetic acid, and the results demonstrate that the ethane groups incorporated in the mesoporous framework have a positive influence on the catalytic behavior of the materials.

Preparation of monolithic silica column with strong cation-exchange stationary phase for capillary electrochromatography

A monolithic silica based strong cation-exchange stationary phase was successfully prepared for capillary electrochromatography. The monolithic silica matrix from a sol-gel process was chemically modified by treatment with 3-mercaptopropyltrimethoxysilane followed by a chemical oxidation procedure to produce the desired function. The strong cation-exchange stationary phase was characterized by its substantial and stable electroosmotic flow (EOF), and it was observed that the EOF value of the prepared column remained almost unchanged at different buffer pH values and slowly decreased with increasing phosphate concentration in the mobile phase. The monolithic silica column with strong cation-exchange stationary phase has been successfully employed in the electrochromatographic separation of beta-blockers and alkaloids extracted from traditional Chinese medicines (TCMs). The column efficiencies for the tested beta-blockers varied from 210,000 to 340,000 plates/m. A peak compression effect was observed for atenolol with the mobile phase having a low phosphate concentration.

Electrochromatographic evaluation of a silica monolith capillary column for separation of basic pharmaceuticals

A silica-based monolithic capillary column was prepared via a sol-gel process. The continuous skeleton and large through-pore structure were characterized by scanning electron microscopy (SEM). The native silica monolith has been successfully employed in the electrochromatographic separation of beta-blockers and alkaloids extracted from traditional Chinese medicines (TCMs). Column efficiencies greater than 250000 plates/m for capillary electrochromatography (CEC) separation of basic compounds were obtained. It was observed that retention of basic pharmaceuticals on the silica monolith was mainly contributed by a cation-exchange mechanism. Other retention mechanisms including reversed-phase and normal-phase mechanisms and electrophoresis of basic compounds also played a role in separation. A comparison of the differences between CEC and capillary zone electrophoresis (CZE) separation was also discussed.

Improved performance of comprehensive two-dimensional HPLC separation of traditional Chinese medicines by using a silica monolithic column and normalization of peak heights

Performance of comprehensive two-dimensional liquid chromatography system is greatly improved than we reported previously by using a silica monolithic column as for the second dimensional separation. Due to the increase of the elution speed on the second dimensional monolithic column, the first dimensional column efficiency and analysis rate can be greatly improved as comparing with conventionally second dimensional column. The developed system was applied to analysis of methanol extraction of two umbelliferae herbs Ligusticum chuanxiong Hort. and Angelica sinensis (Oliv.) Diels by using CN column as for the first dimensional separation and a silica monolithic ODS column for the second dimensional separation, and the obtained three-dimensional chromatograms were treated by normalization of peak heights with the value of the highest peak or setting a certain value using a software written in-house. It was observed that much more peaks for low-abundant components in TCM extract can clearly be detected here than we reported before, due to the large difference for the amount of components in TCMs' extract. With the above improvements in separation performance and data treatment, totally about 120 components in methanol extraction of Rhizoma chuanxiong and 100 in A. sinensis were separated with UV detection within 130 min. This result meant that both the number of peaks detected increase twice but the analysis time decease twice if comparing with the previously reported result. (c) 2005 Published by Elsevier B.V.