MCM-41的制备及用于吡拉西坦缓释性能研究

以十六烷基三甲基溴化铵（CTAB）为模板剂,正硅酸乙酯（TEOS）为硅源,合成MCM-41分子筛.以其做载体,吡拉西坦为模型药物,研究了吡拉西坦在MCM-41分子筛的负载与释放性能.并通过扫描电子显微镜（SEM）、粉末X-射线衍射（XRD）和傅立叶变换红外光谱（FT-IR）等方法对MCM-41分子筛以及负载吡拉西坦后的样品进行表征.研究了吡拉西坦的负载量及释放性能,定时检测了制备药物在模拟体液中的释放过程,从而确定以MCM-41作为吡拉西坦缓释载体的可能性.     

Adsorption of Bovine Serum Albumin and lysozyme on siliceous MCM-41

The adsorption of Bovine Serum Albumin (BSA) and lysozyme on MCM-41 was studied. In particular, characteristics important to the use of this adsorbent as a chromatographic support for protein separations have been examined. These include the effects of external surface area, solution conditions (pH), and rate of adsorption. Comparative studies were performed on MCM-41 of three pore sizes (24.8 Å, 36 Å, 53.5 Å). It has been shown that differences in external surface area can strongly influence the adsorption capacity. This implies that adsorption on the external surface can be misinterpreted as adsorption in the pores of MCM-41. Thus, high adsorption capacities may not necessarily mean high molecular-sieving capacities. This paper also reports a dependence of protein uptake rates on solution conditions. Calorimetry suggests that under certain solution conditions the adsorption of BSA is a combination of two sequential energetic events. These are postulated to be BSA adsorption followed by reorientation/reconformation of the adsorbed protein on the surface. The slow second step affects the attainment of equilibrium.     

The entrapment of UO2 in mesoporous MCM-41 and MCM-48 molecular sieves

A method based on direct template-ion-exchange was employed for the entrapment of UO₂²⁺ ions in MCM-41 and MCM-48 molecular sieves via swapping of cetyltrimethylammonium cations present in the mesoporous channels by the UO₂²⁺ ions in an aqueous solution. The samples were characterized by XRD, FT-IR, and ICP-AES techniques. The entrapment of UO₂²⁺ ions is facilitated by the large pore size vis-a-vis the high surfactant content in the as-synthesized host materials. A higher loading of UO₂²⁺ ions was achieved in MCM-48 as compared to MCM-41, which could be attributed to its three-dimensional pore system and higher surfactant-to-silica ratio. FT-IR results provide an evidence of a strong binding of UO₂²⁺ groups with the defect silica sites of mesoporous molecular sieves.     

Preparation of spherical MCM-41 molecular sieve at room temperature: Influence of the synthesis conditions in the structural properties

A rapid and facile synthesis route to obtain mesoporous MCM-41 silica at room temperature under basic conditions using as template cetyltrimethylammonium bromide (CTAB) is reported. The synthesis variables such as reaction time, molar ratios of CTAB/TEOS and H₂O/ethanol in the initial gel composition were studied. Samples were characterized by X-ray diffraction, nitrogen adsorption–desorption analyses, scanning electron microscopy and transmission electron microscopy. It was found that reaction conditions affect the quality of the MCM-41 silica. This silica can be prepared at short periods of time, and it exhibited a uniform size and spherical morphology.     

Effect of pH in hydrothermal treatment of as-synthesized MCM-41 on wetting stability of resulting materials in aqueous solution

Effect of pH in aqueous media used in the hydrothermal treatment of as-synthesized MCM-41 on the structure and the wetting stability of the resulting materials was studied using XRD, TG-DTA and N₂ adsorption. The long-range structural order and the wetting stability of the mesoporous MCM-41 were improved through hydrothermal treatment of as-synthesized sample at around pH 7 without salt addition. The pH adjustment of aqueous media toward neutral is thought to shift the polymerization equilibrium of silica species around external surface of the micelles to a higher degree of condensation, and to reduce the electrostatic repulsion between the silicate–micelle composites. This leads to the further formation of Si–O–Si network within the silica walls of the mesoporous materials, resulting in the enhancement of the structural stability of MCM-41 samples.     

MCM-41分子筛的制备及催化性能研究

用微波法合成MCM-41中孔分子筛.并采用液相沉积法制备了以MCM-41分子筛为载体负载TiO2/S2O82-的同体酸催化剂,以乙酸与异戊醇的酯化反应作为探针反应,考察了焙烧温度、焙烧时间、浸渍溶液的浓度、浸渍时间以及钛硅比等制备条件对催化剂催化活性的影响,得到了最佳的制备条件.最佳条件是:n(Ti)/n(Si)=2,...     

微波法合成MCM-41介孔分子筛及吸附性能研究

以十六烷基三甲基氯化铵为模板剂,在微波实验条件下合成MCM-41介孔分子筛,缩短了合成时间,降低产品成本。实验考察了多种因素对MCM-41合成的影响,并通过吸附处理亚甲基蓝溶液能力强弱,得到最佳合成条件：摩尔比1TEOS：0.2CTMACl：160H2O,pH为10,晶化时间15 min。通过红外光谱分析,MCM-41分子筛的主要特征吸收峰均已出现,说明合成分子筛MCM-41成功。     

Efficient isomerization of safrole by amino-grafted MCM-41 materials as basic catalysts

Design of base catalyst featuring large mesoporous surfaces allows performing base-catalysed reactions in the fields of production of perfumes. Post-synthesis grafting of organotrialkoxysilanes has effectively been applied to incorporate active organic functional groups onto the mesoporous silica surfaces. The novelty of our study is the use of mesoporous materials with different chemical compositions: silicate (MCM-41), aluminosilicate (AlMCM-41; Si/Al = 64) and niobosilicate (NbMCM-41; Si/Nb = 64) and consequently, different acidity, as supports for three aminopropylalkoxysilanes (APMS), [3-(2-aminoethylamino) propyl]trimethoxysilane (2APMS) and 3-[2-(2-aminoethylamino) ethylamino]propyltrimethoxysilane (3APMS). Isomerization of safrole to the corresponding thermodynamically stable isosafrole has been carried out on these amino-grafted MCM-41 materials. Maximum conversion of around 85% with a cis/trans ratio of 1/9 at 433 K in DMF as solvent was obtained. Isomerization is strongly dependent on the nature of the support and changed in the following order: APMS/AlMCM-41 > APMS/NbMCM-41 ? APMS/MCM-41. The nature of the amine chain is also responsible of the activity. The order of activity is APMS/AlMCM-41 > 2APMS/AlMCM-41 > 3APMS/AlMCM-41.     

MCM-41纳米粒子的制备

以十六烷基三甲基溴化铵(CTAB)为模板剂,通过添加MCM-41前驱体合成了MCM-41纳米粒子,采用XRD、SEM、FTIR等手段对样品进行了分析表征。结果表明加入MCM-41前驱体合成的固体产物具有MCM-41特有的六方排列的孔道结构和较高的有序度,所合成的MCM-41平均粒径为70 nm。     

Pyrolysis of Polyethylene over Aluminum-Incorporated MCM-41 Catalyst

Aluminum-containing MCM-41 catalysts were synthesized in this study by impregnation of aluminum into hydrothermally synthesized MCM-41. Aluminum was loaded into the porous framework of silica with different Al/Si ratios, using aluminum isopropoxide as the aluminum source. These catalysts exhibited Type IV adsorption–desorption isotherms and had a pore diameter of 2.4 nm. Aluminum species were coordinated tetra- and octahedrally in the structure of catalysts. Diffuse Reflectance Fourier Transform Infrared Spectra (DRIFTS) analysis of the pyridine-adsorbed catalysts revealed the existence of Brönsted acid sites in the synthesized catalysts in addition to the Lewis acid sites. The performance of these catalysts was tested in the degradation of polyethylene using a thermogravimetric analyzer. Pure MCM-41 did not show a significant reduction in the degradation temperature of polyethylene, whereas aluminum-impregnated catalysts were successful in decreasing the temperature.     

介孔分子筛MCM-41在有机催化中的研究进展

介绍了近几年MCM-41在环氧化、加氢反应、烷基化、酯化等有机反应中的应用。介孔分子筛MCM-41具有较高的比表面和规整的结构,以及表面带有羟基,是催化剂的优良载体。因此,可以将催化剂引入到MCM-41的结构中,从而提高其性能。认为应在介孔分子筛的水热稳定性、研究合成机理、合成方法等方面加强研究,对介孔分子筛在有机化工催化领域中的应用现状及前景进行了分析。     

MCM—41中孔分子筛的研究和开发

介绍了近期国内外中孔分子筛ＭＣＭ－４１的研究情况，阐述了其合成机理并简述了其性能和应用。     

MCM-41-HY介孔-微孔复合分子筛的水热合成

以微孔分子筛HY浆液为母液,合成介孔-微孔复合分子筛MCM-41-HY。通过XRD、NH_3-TPD和N_2吸附-脱附等手段对复合材料进行了表征,并对复合分子筛的水热稳定性进行了考察。结果表明,复合分子筛MCM-41-HY具有中孔分子筛MCM-41和微孔HY型沸石的特点,并且与纯MCM-41分子筛相比,复合分子筛的酸强度明显增强,水热稳定性提高。     

Synthesis of aluminum rich MCM-41

The synthesis of MCM-41 mesoporous compounds with Si/Al ratios as low as 2 without observing the presence of octahedral Al in²⁷AlMAS NMR is reported. FTIR spectra of chemisorbed pyridine indicated that MCM-41 materials in their protonated form exhibit both Brønsted and Lewis acid sites.     

粉煤灰合成中孔分子筛MCM-41及其吸附性能

以粉煤灰为初始原料,十六烷基三甲基溴化铵（CTAB）为模板剂采用水热法合成出中孔分子筛MCM-41,采用小角XRD、TEM、氮气吸附-脱附等对样品的物相、比表面积、孔径、孔体积等进行表征,并研究了样品分子筛对镍离子的吸附性能。结果表明：样品具有典型中孔分子筛MCM-41的特性,比表面积为576 m^2/g,平均孔径为5.53 nm;Ni^2＋能定量吸附在样品分子筛上,最大去除率可达到96%,吸附性能符合Langmuir吸附方程特征,并且随吸附液pH的增大,Ni^2＋去除率也随之增加。     

含铁MCM-41的合成与表征

实验采用液相沉积方式,向MCM-41有序介孔微球的介孔中引入铁盐,通过加热使铁盐分解,铁以氧化物纳米颗粒或Fe-O纳米团簇的形式存在于有序介孔微球的介孔中,从而获得含铁MCM-41有序介孔微球.对不同铁含量的MCM-41进行了比较性表征,并研究了不同铁源对含铁MCM-41合成的影响.研究表明,以Fe(acac)₃的甲苯溶液和Fe(NO₃)₃的水溶液为铁源时,所得试样中铁的含量均随铁离子浓度的增大而增大.铁离子浓度相同时,由前者所得试样的载铁量是后者的3～4倍,最大铁负载量达1 mmol•g^-1.载铁后,有序介孔微球的比表面积、孔容和孔径均减小.以Fe(NO₃)₃的水溶液为铁源时,载铁前驱体试样煅烧后,MCM-41的硅氧骨架发生收缩,而以Fe(acac)₃的甲苯溶液为铁源时,MCM-41的硅氧骨架未见变化.因此,从载铁量及负载过程对有序介孔材料骨架结构的影响看,Fe(acac)₃的甲苯溶液作为铁源用于合成含铁MCM-41优于Fe(NO₃)₃的水溶液.     

Characterizations of aluminum-promoted sulfated zirconia on mesoporous MCM-41 silica: Butane isomerization

Sulfated zirconia (SZ) was supported on mesoporous molecular sieves MCM-41 by impregnation of zirconium sulfate followed by calcination. The nanochannels of MCM-41 provide a large surface area for the solid state dispersion of zirconium sulfate and a steric restriction on formation of zirconia nanoparticles. The catalysts were tested in n-butane isomerization. With the addition of a proper amount of alumina as a promoter, denoted as ASZ/MCM-41, the catalytic activity was dramatically improved in comparison to the activities of SZ/MCM-41. The increase of activity was determined primarily by the amount of aluminum added and the temperature of calcination. The SZ/MCM-41 catalysts were characterized by X-ray diffraction (XRD), high resolution TEM (HR-TEM), NH₃ adsorption (NH₃-TPD), X-ray photoelectron spectroscopy (XPS) and X-ray absorption (EXAFS). In particular, the Zr K-edge EXAFS data give one a measure of the degree of dispersion of zirconia on the surface of MCM-41. The trend of the promotion effects of alumina on SZ in butane isomerization is not monotonic; there is an optimum level of Al-loading for high activity. It is explained based on three quantitative factors: increased sulfur loadings, balanced distribution of Lewis and Brønsted acid sites, and higher dispersion of zirconia.     

Mechanical Stability of Mesoporous Materials, MCM-48 and MCM-41

The structural collapse of mesoporous molecular sieves, MCM-48 and MCM-41 materials by mechanical compression was found to occur mechanochemically through hydrolysis of Si–O–Si bonds. Their ordered structures were retained by compressing the well-dried samples under dry N2. Trimethylsilylation of mesoporous materials proved effective in eliminating their instability to compression through enhancing hydrophobicity.     

Cobalt oxide nanoparticles on mesoporous MCM-41 and Al-MCM-41 by supercritical CO2 deposition

CoO and Co₃O₄ nanoparticles were uniformly dispersed inside mesoporous MCM-41 and Al-MCM-41 supports using supercritical CO₂ reactive deposition. This method represents a one-pot reproducible procedure that allows the dissolution of the organocobalt precursor and supports impregnation in supercritical CO₂ at 70 °C and 110 bar, followed by the precursor thermal decomposition into cobalt species at 200 °C and 160 bar. By the relative concentration of the cobalt precursor [cobalt (II) bis (η⁵-ciclopentadienil)], the load of cobalt nanoparticles was controlled and then determined by Inductively Coupled Plasma (ICP-OES). The synthesis of CoO and Co₃O₄ species inside the MCM-41 and Al-MCM-41 substrates was confirmed by X-ray Photoelectron (XPS) and Laser Raman Spectroscopies (LRS). By N₂ adsorption and Small Angle X-ray Scattering (SAXS), it was determined that the hexagonal arrangement as well as the surface area and pore size of the substrates changed after the addition of cobalt. By means of X-ray mapping from SEM images, a homogeneous distribution of cobalt nanoparticles was observed inside the mesopores when the cobalt loading was 1 wt.%. In addition, spherical cobalt nanoparticles of average diameter close to 20 nm were detected on the outer surface of MCM-41 and Al-MCM-41 supports when the cobalt content was higher. On the other hand, by Transmission Electron Microscopy (TEM), it was possible to measure the interplanar distance of the crystalline plane of the outer nanoparticles, which was later compared with the theoretical distance values which allowed identifying the CoO and Co₃O₄ phases.     

MCM-41介孔分子筛负载咔唑类荧光分子杂化材料的合成及发光性质

通过浸渍法将5种咔唑类荧光分子负载于介孔材料MCM-41上,制备有机-无机杂化复合荧光材料,并对咔唑荧光分子和杂化复合材料的表面结构、紫外-可见吸收、荧光发射等性质进行了对比。结果表明,负载后的咔唑类荧光分子分散于MCM-41孔道上,材料热稳定性提高,在100~350℃内没有明显失重,其紫外吸收和荧光发射也发生明显蓝移(λmaxabs=331~368 nm,λmaxem=401~435 nm)。制备的杂化复合材料可用作蓝色荧光材料(λmaxem=401~435 nm)。