Mesoporous aluminosilicates with ordered hexagonal structure, strong acidity, and extraordinary hydrothermal stability at high temperatures.

Highly ordered hexagonal mesoporous aluminosilicates (MAS-5) with uniform pore sizes have been successfully synthesized from assembly of preformed aluminosilcate precursors with cetyltrimethylammonium bromide (CTAB) surfactant. The aluminosilicate precursors were obtained by heating, at 100--140 degrees C for 2--10 h, aluminasilica gels at the Al(2)O(3)/SiO(2)/TEAOH/H(2)O molar ratios of 1.0/7.0--350/10.0--33.0/500--2000. Mesoporous MAS-5 shows extraordinary stability both in boiling water (over 300 h) and in steam (800 degrees C for 2 h). Temperature-programmed desorption of ammonia shows that the acidic strength of MAS-5 is much higher than that of MCM-41 and is comparable to that of microporous Beta zeolite. In catalytic cracking of 1,3,5-triisopropylbenzene and alkylation of isobutane with butene, MAS-5 exhibits greater catalytic activity and selectivity, as compared with MCM-41 and HZSM-5. The MAS-5 samples were characterized with infrared, UV--Raman, and NMR spectroscopy and numerous other techniques. The results suggest that MAS-5 consists of both mesopores and micropores and that the pore walls of MAS-5 contain primary and secondary structural building units, similar to those of microporous zeolites. Such unique structural features might be responsible for the observed strong acidity and high thermal stability of the mesoporous aluminosilicates with well-ordered hexagonal symmetry.     

The proapoptotic G41S mutation to human cytochrome c alters the heme electronic structure and increases the electron self-exchange rate

The naturally occurring G41S mutation to human (Hs) cytochrome (cyt) c enhances apoptotic activity based upon previous in vitro and in vivo studies, but the molecular mechanism underlying this enhancement remains unknown. Here, X-ray crystallography, nuclear magnetic resonance (NMR) spectroscopy, and density functional theory (DFT) calculations have been used to identify the structural and electronic differences between wild-type (WT) and G41S Hs cyt c. S41 is part of the hydrogen bonding network for propionate 7 of heme pyrrole ring A in the X-ray structure of G41S Hs cyt c and, compared to WT, G41S Hs cyt c has increased spin density on pyrrole ring C and a faster electron self-exchange rate. DFT calculations illustrate an electronic mechanism where structural changes near ring A can result in electronic changes at ring C. Since ring C is part of the solvent-exposed protein surface, we propose that this heme electronic structure change may ultimately be responsible for the enhanced proapoptotic activity of G41S Hs cyt c.     

Incorporation of CdS Nanoparticles Formed in Reverse Micelles into Mesoporous Silica

The incorporation of CdS nanoparticles, prepared in reverse micellar systems, into thiol-modified mesoporous silica, such as FM41 (functionalized MCM-41) and FM48 (functionalized MCM-48), has been investigated. The nanoparticles were immobilized in the mesopores via the incorporation of water droplets of the reverse micelles. A particle-sieving effect for FM41 having large (L-FM41, 3.8 nm) and medium (M-FM41, 3.6 nm) pore size was observed, in that the incorporation of the CdS nanoparticles was decreased with increasing particle size and with decreasing pore size of the FM41. Chemical vapor deposition treatment employed to narrow the mesopores of the CdS-FM41 enhanced the stability of CdS nanoparticles against heat treatment. The CdS-FM41 composites demonstrated photocatalytic activity for H(2) generation from 2-propanol aqueous solution, the better photocatalytic activity being obtained with the larger pore size for CdS-L-FM41. Copyright 2001 Academic Press.     

PtSn/Al2O3/MCM-41催化剂的丙烷脱氢催化性能

用微型催化反应装置评价, 并结合X射线粉末衍射(XRD)、表面积和孔结构测试、程序升温还原(TPR)、氢化学吸附和热重分析等方法研究了负载型PtSn/γ-Al2O3, PtSn/MCM-41和PtSn/Al2O3/MCM-41催化剂的丙烷脱氢反应催化性能. 发现PtSn/Al2O3/MCM-41催化剂具有较PtSn/MCM-41催化剂高的丙烷脱氢反应活性和较PtSn/γ-Al2O3催化剂高的反应稳定性. 实验结果表明, 纯硅MCM-41载体表面的锡物种因与载体相互作用较弱故易被还原, 导致铂金属分散度和催化剂的丙烷脱氢活性较低. 用Al2O3修饰MCM-41可以增强Sn物种与Al2O3/MCM-41载体之间的相互作用, 提高PtSn/Al2O3/MCM-41催化剂铂金属分散度和丙烷脱氢催化活性. 并且, 积炭后的PtSn/Al2O3/MCM-41催化剂具有较高的铂金属表面裸露度, 故具有较高的丙烷脱氢反应稳定性. PtSn/Al2O3/MCM-41催化剂优良的丙烷脱氢催化性能可能不仅与Sn-载体Al2O3/MCM-41较强的相互作用有关, 而且与Al2O3/MCM-41载体的介孔结构有关.     

Striking Improvement in Peroxidase Activity of Cytochrome c by Modulating Hydrophobicity of Surface‐Functionalized Gold Nanoparticles within Cationic Reverse Micelles

This work demonstrates a remarkable enhancement in the peroxidase activity of mitochondrial membrane protein cytochrome c (cyt c) by perturbing its tertiary structure in the presence of surface‐functionalised gold nanoparticles (GNPs) within cetyltrimethylammonium bromide (CTAB) reverse micelles. The loss in the tertiary structure of cyt c exposes its heme moiety (which is buried inside in the native globular form), which provides greater substrate (pyrogallol and H₂O₂) accessibility to the reactive heme residue. The surfactant shell of the CTAB reverse micelle in the presence of co‐surfactant (n‐hexanol) exerted higher crowding effects on the interfacially bound cyt c than similar anionic systems. The congested interface led to protein unfolding, which resulted in a 56‐fold higher peroxidase activity of cyt c than that in water. Further perturbation in the protein’s structure was achieved by doping amphiphile‐capped GNPs with varying hydrophobicities in the water pool of the reverse micelles. The hydrophobic moiety on the surface of the GNPs was directed towards the interfacial region, which induced major steric strain at the interface. Consequently, interaction of the protein with the hydrophobic domain of the amphiphile further disrupted its tertiary structure, which led to better opening up of the heme residue and, thereby, superior activity of the cyt c. The cyt c activity in the reverse micelles proportionately enhanced with an increase in the hydrophobicity of the GNP‐capping amphiphiles. A rigid cholesterol moiety as the hydrophobic end group of the GNP strikingly improved the cyt c activity by up to 200‐fold relative to that found in aqueous buffer. Fluorescence studies with both a tryptophan residue (Trp59) of the native protein and the sodium salt of fluorescein delineated the crucial role of the hydrophobicity of the GNP‐capping amphiphiles in improving the peroxidase activity of cyt c by unfolding its tertiary structure within the reverse micelles.     

Gas adsorption in mesoporous micelle-templated silicas: MCM-41, MCM-48, and SBA-15

This paper reports a molecular simulation and experimental study on the adsorption and condensation of simple fluids in mesoporous micelle-templated silicas MCM-41, MCM-48, and SBA-15. MCM-41 is described as a regular cylindrical silica nanopore, while SBA-15 is assumed to be made up of cylindrical nanopores that are connected through lateral channels. The 3D-connected topology of MCM-48 is described using a gyroid periodic minimal surface. Argon adsorption at 77 K is calculated for the three materials using Grand Canonical Monte Carlo simulations. Qualitative comparison with experiments for nitrogen adsorption in mesoporous micelle-templated silicas is made. The adsorption isotherm for SBA-15 resembles that for MCM-41. In particular, capillary condensation and evaporation are not affected by the presence of the connecting lateral channels. In contrast, the argon adsorption isotherm for MCM-48 departs from that for MCM-41 having the same pore size. While condensation in MCM-41 is a one-step process, filling of MCM-48 involves two successive jumps in the adsorbed amounts which correspond to condensation in different domains of the porosity. The condensation pressure for MCM-48 is larger than that for MCM-41. We attribute this result to the morphology of the MCM-48 surface (made up of both concave and convex regions) that differs from that for MCM-41 (concave only). Our results suggest that the pore connectivity affects pore filling when the size of the connections is comparable to that of the nanopores.     

The Synthesis and Application of the Mesoporous Molecular Sieves MCM-41 — A Review

We report a “delayed neutralization” process for the preparation of highly-ordered aluminosilicate MCM-41 molecular sieves with high thermal and hydrothermal stability, and sharp pore size distribution. However, the structural order and pore size are dependent on the carbon chain length. In the mixture surfactant systems, the pore size of the MCM-41 materials could be fine-tuned. The pore size can be extended from 2.5 to 4.5 nm by adding a suitable amount of hydrocarbons. The tubular morphology of the MCM-41 material of 0.3 to 10 micrometers diameter, where the wall consists of coaxial cylindrical pores of nanometers MCM-41, can be obtained by careful control of the surfactant-water content and the rate of condensation of silica. An optimum condition for automatic synthesis of the hierarchical TWT structure has been accomplished. The addition of 1-alkanols as cosurfactant would not only improve the order of the MCM-41 hexagonal structure but also promote the formation of micrometer-sized hierarchical materials, for example: tubules-within-tubule and uniform-sized hollow spheres of diameter 5.0 ± 1.0 μm. However, the inside of the micron spheres has intricate structures possessing various topological genus ranks. The MCM-41 is a good supporter for Molybdenum oxide catalysts. The rate of deactivation in the catalytic reaction of ethyl-benzene dehydrogenation to styrene increases in the order: M_T < M_P < SiO₂. The physically mixed samples have higher catalytic activity than impregnated ones.     

Remarkable effect of pore size on the catalytic activity of mesoporous silica for the acetalization of cyclohexanone with methanol

The catalytic activity of mesoporous silica (MCM-41) for the acetalization of cyclohexanone shows a volcano-shaped dependence on the pore diameter. The diameter of the cyclohexanone molecule is ca. 0.75 nm, while its acetalization with methanol was well accelerated on MCM-41 with a pore diameter of approximately 1.9 nm, and smaller or larger pores were not suitable for the catalysis. The catalytic activity was independent of the Al concentration.     

Redox reaction of PEO modified cytochrome c adsorbed on the electrode in ion conductive PEO matrix analyzed with non-contact optical waveguide spectroscopy

Optical waveguide spectroscopy was used under non-contact conditions to analyze the visible absorption spectrum of poly(ethylene oxide) (M _w = 150) modified cytochrome c (PEO₁₅₀-cyt.c) adsorbed on an indium tin oxide (ITO) glass electrode. The redox reactions of the adsorbed PEO₁₅₀-cyt.c were dynamically measured in situ in PEO oligomers (M _w = 200). It was confirmed that PEO modification of cyt.c is effective in maintaining the redox activity of the cyt.c after adsorption on the ITO glass electrode. The PEO₁₅₀-cyt.c adsorbed on the electrode re-dissolved gradually in PEO oligomer. Against this, PEO₁₀₀₀-cyt.c having longer PEO chains (M _w = 1000) was found to be adsorbed stably on the electrode. Copyright © 2003 John Wiley & Sons, Ltd.     

Synthesis of stearic acid triethanolamine ester over solid acid catalysts

<正>The synthesis of stearic acid triethanolamine ester over solid acid catalysts was investigated.The results showed that the catalytic activity and selectivity of zirconium sulfate supported on SBA-15(6)(pore diameter 6 nm) is better than that of commonly used hypophosphorous acid,zirconium sulfate supported on MCM-41 and zirconium sulfate supported on SBA-15(9)(pore diameter 9 nm).     

NO reductase activity of the tetraheme cytochrome C554 of Nitrosomonas europaea

The tetraheme cytochrome c(554) (cyt c(554)) from Nitrosomonas europaea is believed to function as an electron-transfer protein from hydroxylamine oxidoreductase (HAO). We show here that cyt c(554) also has significant NO reductase activity. The protein contains one high-spin and three low-spin c-type hemes. HAO catalyzed reduction of the cyt c(554), ligand binding, intermolecular electron transfer, and kinetics of NO reduction by cyt c(554) have been investigated. We detect the formation of a NO-bound ferrous heme species in cyt c(554) by EPR and M?ssbauer spectroscopies during the HAO catalyzed oxidation of hydroxylamine, indicating that N-oxide intermediates produced from HAO readily bind to cyt c(554). In the half-reduced state of cyt c(554), we detect a spin interaction between the [FeNO](7) state of heme 2 and the low-spin ferric state of heme 4. We find that ferrous cyt c(554) will reduce NO at a rate greater than 16 s(-1), which is comparable to rates of other known NO reductases. Carbon monoxide or nitrite are shown not to bind to the reduced protein, and previous results indicate the reactions with O(2) are slow and that a variety of ligands will not bind in the oxidized state. Thus, the enzymatic site is highly selective for NO. The NO reductase activity of cyt c(554) may be important during ammonia oxidation in N. europaea at low oxygen concentrations to detoxify NO produced by reduction of nitrite or incomplete oxidation of hydroxylamine.     

Co掺杂ZnO/MCM-41分子筛的制备及对异戊醇的催化氧化性能

以Co掺杂的介孔分子筛MCM-41为载体, 采用等体积浸渍法制备了系列5%ZnO/xCo-MCM-41催化剂, 并用于催化分子氧氧化异戊醇合成异戊醛的反应. 通过X射线衍射(XRD), 傅里叶变换红外光谱(FTIR), 紫外-可见漫反射光谱(UV-Vis DRS), 扫描电子显微镜(SEM), 氨气程序升温脱附(NH₃-TPD), 氢气程序升温还原(H₂-TPR)和氮气吸附-脱附等手段对样品进行表征, 并考察了Co掺杂量对分子筛结构和催化性能的影响. 结果表明, 随着Co掺杂量的增大, 样品的比表面积和孔体积均减小, 而其平均孔径呈先增大后减小的趋势. 当Co掺杂量为0.05时, 5%ZnO/0.05Co-MCM-41仍保持了MCM-41高度有序的六方介孔结构, 具有高比表面积(989 m²/g)、较大孔径(2.88 nm)和孔体积(0.88 cm³/g), 引入的Co主要以孤立态钴离子[Single-site Co(Ⅱ)]形式存在于MCM-41骨架, MCM-41骨架中的Co可以有效提高ZnO微粒的分散度, 适度降低5%ZnO/MCM-41的表面酸性, 并大幅度提高5%ZnO/MCM-41的氧化还原性. 与5%ZnO/MCM-41相比, 5%ZnO/0.05Co-MCM-41可使异戊醛的选择性提高28.3%.     

Heterogeneous chiral Mn(III) salen catalysts for the epoxidation of unfunctionalized olefins immobilized on mesoporous materials with different pore sizes

Two chiral Mn(III) salen complexes were immobilized onto a series of mesoporous MCM-41 and MCM-48 materials with different pore sizes and the as-synthesized catalysts were active and enantioselective for the asymmetric epoxidation of styrene and indene. The results of XRD, FTIR, DR UV-vis, and N₂ sorption showed that the chiral Mn(III) salen complexes were anchored in the channels of mesoporous materials. The influence of organic silicane dosage on the catalytic performance was studied and the optimum dosage of organic silicane for preparing heterogeneous catalysts was determined. Furthermore, the effect of the fine-tuning of pore size on the performance of heterogeneous catalysts was discussed. In general, larger pore size of the supports could lead to higher conversions and the compatible pore size with substrate may be responsible for the improved enantiomeric excess (ee) values.     

Synthesis,characterization and potential applications of new materials in the mesoporous range

M41S is the designation of a new type of mesoporous structures. The characteristics of these materials are large surface areas and very narrow pore size distributions, with pore diameters tunable from 15 to 100 Å. The M41S family consists of MCM-48, which has a cubic ordered pore structure, MCM-41, which has a hexagonally ordered pore structure and MCM-50, which has an unstable lamellar structure. In this review we cover the synthesis, modification, characterization and potential applications of these materials.     

Synthesis and Characterization of Ce-Containing MCM-41

SUMMARY. The cerium-containing MCM-41 (Ce-MCM-41) has been synthesized with size in the micrometer range by direct hydrothermal method. Transmission electron microscopy shows the regular hexagonal array of uniform channel characteristics of MCM-41. Five peaks were detected in the lov-angle XRD patterns,an interplanar spacing d100 = 40.6 A was obtained that can be indexed on a hexagonal unit cell with a0 = 46.9 A. Nitrogen adsorption isotherm at 77 K revealed a surface area of 920 m2/g, pore size of 26.2 A and wall thickness of 18.1 A. A cell contraction of 2.6 A upon calcination was observed. The spectroscopic studies indicate that the synthesized sample is with MCM-41 structure and Ce is in the framework position. A weak Lewis acidity was indicated by infrared spectra of pyridine adsorption. The synthesized Ce-MCM-41 exhibits fairly catalytic activity for the NO reduction by CO.     

以混合表面活性剂为模板可控合成MCM-48和MCM-41分子筛

利用阳离子和三嵌段共聚物混合表面活性剂为模板,在水热条件、碱性介质中可控合成出MCM-48和MCM-41分子筛。在固定P123(聚氧乙烯-聚氧丙烯-聚氧乙烯三嵌段共聚物):TEOS(正硅酸乙酯)(物质的量的比)为0.01875的体系中,调节CTAB(十六烷基三甲基溴化铵)∶TEOS(正硅酸乙酯)物质的量比值m,当m在0.12~0.13范围合成出MCM-48分子筛;当m在0.04~0.08范围合成出MCM-41分子筛。通过XRD,TEM,N2物理吸附,IR等方法进行了表征。结果表明:聚氧乙烯-聚氧丙烯-聚氧乙烯三嵌段共聚物(P123)的加入可以更大程度地降低合成介孔材料所需阳离子表面活性剂的用量;可控合成的介孔材料具有高比表面积、高度有序的孔道结构、较集中的孔径分布。     

Prearation of Highly Ordered Mesoporous Silica Materials and Application as Enzeme Supports

An enzyme, horseradish peroxidase (HRP), was adsorbed in the manner of single immersion method on the silica mesoporous materials, FSM-16, MCM-41 and SBA-15 with various pore diameters from 27 to 92 and their enzymatic activity in an organic solvent and the thermal stability were studied. FSM-16 and MCM-41 showed larger amount of adsorption of HRP than SBA-15 or silica gel,when the pore sizes were larger than the spherical molecular diameter of HRP (ca 64×37). The increased enzyme adsorption capacity may be due to the surface characteristics of FSM-16 and MCM-41, which would be consistent with the observed larger adsorption capacity of cationic pigment compared with anionic pigment for these materials. The immobilized HRP on FSM-16 and MCM-41 with pore diameter above 50 showed the highest enzymatic activity in an organic toluene and thermal stability in aqueous solution at the temperature of 70℃. The immobilized enzymes on the other mesoporous materials including large or small pore sized FSM-16 showed lower enzymatic activity in an organic solvent and the thermal stability. Both surface character and size matching between pore sizes and the molecular diameters of HRP were important in achieving high enzymatic activity in organic solvent and high thermal stability.     

锌锡双金属掺杂MCM-41的合成及表征

以硅酸钠为硅源, 锡酸钠，硝酸锌为金属源，十六烷基三甲基溴化铵为模板剂，采用直接水热合成法合成出了锌锡双金属同时掺杂的介孔MCM-41。通过ICP﹑XRD、TG-DTA﹑FTIR﹑HRTEM以及BET等技术对材料的结构和性质进行了表征。结果表明，合成的材料具有典型的六方介孔结构，比表面高，孔分布窄，热稳定性较高，且锌锡可能进入介孔MCM-41骨架中。该材料对苯酚羟基化反应具有良好的催化性能，双金属修饰MCM-41催化活性明显优于单组分掺杂。     

Spectroscopic monitoring for the formation of mesoporous MCM-41 materials upon microwave irradiation

The mesoporous MCM-41 materials were prepared in very short crystallization time (∼40 min) upon microwave irradiation in comparison with conventional hydrothermal heating method. With both microwave irradiation and hydrothermal heating, the MCM-41 formation via supramolecular templating method has been monitored by fluorescence and electron spin resonance (ESR) spectroscopy. Pyrene as a fluorescence probe and 4-(N,N-dimethyl-N-hexadecyl)ammonium-2,2,6,6-tetramethyl piperidinyloxy iodide (CAT16) as a spin probe were respectively dissolved into the micelle solutions to form the MCM-41 precursor gels. These probes allow the monitoring of the supramolecular interaction between the anionic silicate species and the cationic surfactant molecules during the MCM-41 formation. Analyses of fluorescence and ESR spectra indicate that the fast increase of hydrophobicity and microviscosity at the solubilzation sites of the probes results from the accelerated condensation of silicates onto the micelle surface upon microwave irradiation. The fluorescence change from the silicate L-center in the MCM-41 precursor gel also probes the fast silicate condensation upon microwave irradiation. It seems that the fast formation of MCM-41 upon microwave irradiation is ascribed to the microwave-susceptible head groups of surfactant molecules in addition to fast dissolution of the precursor gel.     

A study of freezing-melting hysteresis of water in different porous materials. Part II: surfactant-templated silicas

The freezing-melting hysteresis of water in mesoporous silicas MCM-48, MCM-41 and SBA-16 has been studied by NMR cryoporometry. The hysteresis in MCM-48 was found to exhibit nearly parallel branches, matching type H1 hysteresis that had been observed earlier in controlled pore glass. The same type of hysteresis is observed in two of three different-sized MCM-41 under study (a pore diameter of 3.6 and 3 nm), superimposed with a secondary, extremely broad, type H3 hysteresis. No hysteresis was found in the smallest MCM-41 with a pore diameter < 3 nm. Finally, water in SBA-16 exhibits type H2 hysteresis with the freezing branch being essentially steeper than the melting one, which is attributed to a pore blockage upon freezing, similar to what we observed earlier in Vycor porous glass. The data were analyzed using the model of curvature-dependent metastability of a solid phase upon melting; the validity of this model has been discussed.