MCM-48中孔分子筛的合成

在文献报道的水热法合成MCM 48中孔分子筛的基础上,针对在不同时期合成MCM 48合成重复性不好的问题,系统地考察了滴加正硅酸乙酯(TEOS)时溶液的温度,发现在溶液温度为20℃时滴加TEOS时配制的合成液能合成出有序性较高的MCM 48,并考察了焙烧温度及气氛对合成MCM 48中孔分子筛的影响,通过XRD、TG/DSC等对合成的产物进行了表征。     

Influence of the reaction conditions on the thermal stability of mesoporous MCM-48 silica obtained at room temperature

The thermal stability of MCM-48 silicas synthesized at room temperature under basic conditions using cetyltrimethylammonium bromide (CTAB) as template was evaluated as a function of the reaction time, CTAB/TEOS and H₂O/ethanol molar ratios and ammonium hydroxide (NH₄OH) concentration in the initial gel composition. Samples were characterized by X-ray diffraction (XRD), nitrogen adsorption–desorption analyses, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). It was found that synthesis conditions affect the structural and thermal properties of the MCM-48 silicas. These silicas exhibited a size from 200 to 500 nm with spherical morphology.     

低模板剂快速合成介孔分子筛MCM-48

采用水热合成法,通过优化合成条件,高温短时间内成功合成了热及水热稳定性较高、有序性较强的介孔分子筛MCM-48,并考察了模板剂十六烷基三甲基溴化铵(CTAB)用量、温度、晶化时间及CTAB和NaF的加入次序对合成MCM-48的影响.通过XRD和SEM对产物进行表征,结果显示:在n(CTAB)/n(Si) =0.1、n(...     

含氟体系中合成条件对MCM-48分子筛结构性能的影响

在合成过程中引入F~-可以缩短MCM-48分子筛的晶化时间,考察以正硅酸乙酯(TEOS)为硅源、十二烷基三甲基溴化铵(CTAB)为模板剂的合成体系中加入F~-后,n(CTAB)∶n(Si)、晶化时间和晶化温度等合成条件对MCM-48结构性能的影响。XRD、N_2吸附脱附和TEM等表征结果表明,在n(CTAB)∶n(Si)=0.65、晶化温度120℃和反应时间24 h条件下,合成的MCM-48分子筛结晶度较高,比表面积为1 305 m~2·g~(-1),平均孔径3.416 nm,为MCM-48分子筛的适宜合成条件。     

MCM-48分子筛催化剂上正庚烷的临氢异构化

制备了Ni-PMo₁₂/MCM-48中孔分子筛催化剂并用于正庚烷异构化反应研究。采用XRD、BET吸附、红外吡啶吸附等方法对催化剂进行表征。研究了反应温度、还原温度、 还原时间和还原氢气流速对异构化催化性能的影响,并考察了催化性能随时间的变化。结果表明,当镍（Ni）和磷钼酸（PMo）质量分数分别为3%和30%、Ni-PMo/MCM-48对正庚烷异构化反应具有较好的异构化性能,还原温度400℃、还原4h、氢气流速为30 mL/min、反应温度300 ℃时,催化剂性能最好,转化率为14.2%时,异构化选择性达到65.6%。     

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.     

Transition metal substituted derivatives of cubic MCM-48 mesoporous molecular sieves

Mesoporous Ti-, Cr- and V-substituted derivatives of the cubic silica molecular sieve MCM-48 have been hydrothermally synthesized at 373 K by an electrostatic assembly pathway using cetyltrimethylammonium cation as the templating agent. The transition metal substituted products all exhibit improved crystallinity and a narrower pore size distribution relative to the pristine molecular sieve. Transition metal substitution caused an enlargement of the cubic unit cell as well as an increase in the degree of crosslinking in the mesopore walls. The coordination of V-sites in the meso-structure is exclusively tetrahedral, as judged by NMR spectroscopy. These sites as well as those of Ti and Cr sites are active and selective for the peroxide oxidation of styrene and methyl methacrylate to benzaldehyde and methyl pyruvate, respectively.     

Ni-PMo_(12)/MCM-48催化剂的制备与催化性能研究

通过水热合成法制备了中孔分子筛MCM-48,并采用等体积浸溃法负载活性组分镍(Ni)和磷钼酸(PMo12).采用XRD、BET吸附、红外吡啶吸附等方法对催化剂进行表征.考察了反应温度、还原温度和还原时间对异构化催化性能的影响及催化性能随反应时间的变化.结果表明,w(Ni)=3%-w(PMo12)=30%/MCM-48对正庚烷异构化反应具有较好的异构化性能,当还原温度400℃、反应温度300℃时,催化剂催化性能最好,转化率为14.2%时,异构化选择性能够达到65.6%.     

MCM-41介孔分子筛改性研究新进展

针对目前研制的MCM-41介孔分子筛因水热稳定性较差、孔径过小、难以用于重油加工等方面的缺陷,综述了国内外对MCM-41介孔分子筛改性研究的新进展,尤其是扩大分子筛孔径、提高水热稳定性、引入杂原子和后处理等方面的最新研究。     

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.     

Acidity and catalytic activity of the mesoporous aluminosilicate molecular sieve MCM-41

The acidity and catalytic properties of aluminosilicate mesoporous molecular sieves with the MCM-41 structure and bulk Si/Al ratios in the 10–60 range have been investigated. The incorporation of 4-coordinate aluminium into the structure of MCM-41 generates both BrØnsted and Lewis acid sites in amounts increasing with the degree of incorporation. However, the BrØnsted/Lewis acid population ratio is independent of the content of aluminium. The number and strength of acid sites generated are comparable to those of a pillared acid-activated clay and lower than in zeolite H-Y with Si/Al=3.65. Aluminosilicate MCM-41 is a moderate catalyst for the conversion of cumene which proceeds predominantly via catalytic cracking to propene and benzene. The sample of MCM-41 with the highest content of framework aluminium (Si/Al=10) has the largest number of BrØnsted acid sites and exhibits highest catalytic activity.     

介孔MCM-48粉体对环氧树脂性能影响

采用溶液共混法制备了介孔MCM-48粉改性环氧树脂复合材料,研究了MCM-48添加量对复合材料力学性能及介电性能的影响。结果表明,添加少量的MCM-48粉能够同时对环氧树脂起到增强增韧效果。复合材料1MHz下的介电常数及介电损耗均随MCM-48添加量的增加先降低后升高。当MCM-48的添加量为2%时,复合材料的综合性能最佳,弯曲强度为82.15 MPa,弯曲弹性模量为2.45 GPa,冲击强度为21.75 kJ/m2,分别比纯环氧树脂提高了27.36%、28.32%、136.59%。复合材料1MHz下的介电常数为3.55,介电损耗为0.028。该材料有望在微电子领域获得应用。     

Application of mesoporous MCM-48 and SBA-15 materials for the separation of biochemicals dissolved in aqueous solution

The application of molecular sieves for the separation and purification of biological molecules has been limited because of their available pore size (>1.3 nm). With the development of synthetic mesoporous materials, the available pore size range (1.5-10 nm) has been extended. They have pores large enough to allow access for a number of biological molecules. This work investigated the use of two mesoporous materials (MCM-48 and SBA-15) with different pore sizes and structures for adsorption of cephalosporin C as a model compound of biological molecules in terms of ethanol concentration, solution pH, and temperature. It was found that these materials have the potential for the separation and purification processes of biochemicals including antibiotics, amino acids, and proteins.     

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.     

有机弱碱体系中介孔分子筛MCM-41的合成与表征

在有机弱碱无水乙二胺为碱介质的条件下(pH≈10) ,以阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)为模板剂,以正硅酸乙酯(TEOS)为硅源,在室温下合成了介孔分子筛MCM-41。与在强碱水热体系中合成的样品相比,室温弱碱体系中合成的样品具有孔道短程有序度高等特点。详细考察了晶化时间、表面活性剂浓度和晶化温度对产物结构的影响。用XRD对所合成的产物进行表征,结果表明,晶化时间越长,所得到产物的有序度越高;随着表面活性剂质量分数的增加,所合成产物的结构和晶型的完整性越高,但并不是表面活性剂的质量分数越大越好,当表面活性剂的质量分数大于6%时,就呈现下降的趋势;随着晶化温度的升高,所得样品的规整性变差,但晶格参数a₀随温度的升高而呈现变大的趋势。     

Synthesis,characterization and catalytic properties of mesoporous MCM-48 containing zeolite secondary building units

Mesoporous aluminosilicate MCM-48 containing zeolite secondary building units in the pore wall has been synthesized in alkaline media with a two-step procedure. The aluminosilicate precursors comprising zeolite secondary building units were first synthesized by carefully controlling reaction conditions and then were assembled using co-templates of gemini surfactant [C₁₈H₃₇N(CH₃)₂(CH₂)₃-N(CH₃)₂C₁₈H₃₇]²⁺ (18-3-18) and triethanolamine (TEA). X-ray Diffraction (XRD) patterns of the as-made samples indicated that highly ordered mesostructured MCM-48 was formed. Transmission Electron Microscopy (TEM) images further verified the formation of MCM-48 with uniform cubic pore channel system having the pore opening diameter of about 25 ?. Compared with the conventionally synthesized MCM-48, the as-synthesized MCM-48 sample showed an adsorption band at 520–600 cm⁻¹ in its FT-IR spectrum, which was assigned to five-membered ring vibration from zeolite structure. This suggested the presence of zeolite building units in the pore wall. N₂ adsorption data showed that the material had a much higher specific surface area (1 200 m²/g) than the conventional MCM-48(1 100 m²/g). Finally, the catalytic performance of the as-made MCM-48 was evaluated by hydrogenation dealkylation reaction of heavy aromatic hydrocarbons. Catalytic results showed that the as-made MCM-48 catalyst exhibited higher conversion than the conventional MCM-48 catalyst. The as-made mesostructured MCM-48 may have a potential catalytic application in the conversion of bulky molecules. Translated from Journal of Fuel Chemistry and Technology, 2006, 34(1): 105–108 [译自: 燃料化学学报]     

用于氧化反应的改性介孔分子筛MCM-41研究进展

主要从金属掺杂、杂多酸负载和有机官能化等方面详细介绍了改性的MCM-41分子筛作为催化剂在氧化反应中的应用情况,分析了其优缺点。今后的研究重点将是进一步提高改性材料MCM-41分子筛的活性,解决活性组分溶脱现象以及水热稳定性等问题。     

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.     

Ti接枝MCM-48对苯羟化反应的化学亲和选择性及化学稳定性研究

合成了具有较好长程结构和孔结构的Si MCM - 48,以合成后表面接枝改性的方法制备了表面Ti含量不同的Ti接枝MCM - 48催化剂 ,通过X射线衍射 (XRD)、低温N2 吸 -脱附、X射线光电子能谱 (XPS)及原子吸收光谱等对催化剂作了表征 ,Ti接枝MCM - 48仍具有良好的长程有序结构和孔结构 ,其比表面积高于 95 0m2 ·g-1,孔径分布窄 ,随Ti接枝量提高 ,最可几孔径由 2 5nm逐渐降低至 1 9nm。将Ti接枝MCM - 48催化剂用于苯羟化反应 ,研究了其苯羟化性能和结构稳定性 ,结果发现 :Ti接枝MCM - 48对苯羟化反应具有一定活性 ,苯酚选择性高于80 % ,且随表面Ti含量增加 ,苯转化率和苯酚选择性提高。反应后催化剂的孔结构、比表面及孔径分布未受到影响 ,长程有序结构稍有改变     

选择性铵离子交换MCM-49分子筛的酸性及催化性能研究

以动态水热合成方法制备了MCM-49分子筛,分别采用硝酸铵和四丙基溴化铵(TPABr)为铵化剂制备了HMCM-49(NH4NO3)和HMCM-49(TPABr)。采用NH3-TPD和乙腈吸附-红外光谱测试对HMCM-49的酸性进行了表征,对比研究了HMCM-49(TPABr)和HMCM-49(NH4NO3)催化苯与丙烯液相烷基化反应的催化性能。与HMCM-49(NH4NO3)相比,HMCM-49(TPABr)的酸强度保持不变,但总酸量和强酸酸量明显降低。调整TPABr离子交换条件,能够获得酸中心主要分布在外表面并具有不同强酸酸量的HMCM-49(TPABr)催化材料。催化反应结果表明,催化活性随着外表面强酸酸量的增加而提高,在140℃、n(苯)∶n(丙烯)=6的条件下HMCM-49(TPABr)的丙烯转化率比HMCM-49(NH4NO3)降低了2.5%,同时异丙苯选择性提高,达到85.47%。