以混合中性-阳离子表面活性剂为模板合成MCM-48

本文首次将中性和阳离子表面活性剂混和(S^0S^+)形成胶束后,共同作为模板剂合成了立方相中孔分子筛,经此途径得到的中孔分子筛材料既具有MCM-48的立方结构,又能体现出更好的热稳定性。混合不同性质的表面活性剂作为模板剂,将是一种制备不同性能的中孔分子筛的有效易行的途径。     

缓冲体系中高热和水热稳定性的MCM-48介孔分子筛的合成

利用混合阳离子-非离子表面活性剂为模板剂在缓冲体系中成功地合成出具有高热和水热稳定性的MCM-48介孔材料. 通过XRD, N₂吸附-脱附, ²⁹Si MAS NMR和 ³¹P MAS NMR等手段对样品进行了表征. 结果表明, 合成的MCM-48材料具有高的比表面积和高度有序的孔道系统. 样品在空气中于900 ℃下焙烧15 h和在600 ℃ 100%水蒸气下处理8～10 h, 仍能保持良好的立方孔道结构, 显示很高的热稳定性和极好的水热稳定性.     

Mixed Cationic‐nonionic Surfactants and pH Adjustment Route to Synthesize High‐quality MCM‐48

Using the mixture of cetyltrimethylammonium bromide (CTAB) and p‐Octyl polyethylene glycol phenyl ether (OP‐10) as templates, siliceous MCM‐48 materials can be synthesized with low molar ratio of CTAB to silica (0.139:1) and low concentration of mixed surfactants (ca.5%) and within a wide range of OP‐10/CTAB ratio (0.08?0.25). The materials were characterized by X‐ray powder diffraction, N₂ adsorption/desorption isotherm, TEM, TG‐DSC and ²⁹Si MAS NMR. Measurements indicated that the use of mixed surfactants allowed better condensation and higher ordering of the cubic mesostructure; at the same time, some properties of these materials were sensitive to the OP‐10/CTAB ratio. It was also found that the reduced pH of the gel which had been crystallized for a certain time gave a highly reproducible synthesis with a high silica yield (about 95%). Furthermore, the reaction mechanism of the synthesis is discussed in detail.     

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。     

Synthesis of MCM-48 from silatrane via sol–gel process

High-quality cubic MCM-48 is successfully synthesized using a new silica source known as silatrane and cetyltrimethylammonium bromide (CTAB) as the structure-directing agent via sol–gel process. The effects of synthesis parameters, viz. crystallization temperature, crystallization time, surfactant concentration, quantity of NaOH, and silica source, on the product structure are investigated. The synthesized samples are characterized using X-ray diffractometer (XRD), N₂ adsorption–desorption isotherms, and electron microscopy. Optimally, this product is synthesized from samples crystallized at 140°C for 16 h with a CTAB/SiO₂ ratio of 0.3 and NaOH/SiO₂ ratio of 0.5. The XRD result exhibits a well-resolved pattern, corresponding to the Ia3d space group of MCM-48. The BET surface area of this product is as high as 1,300 m²/g with a narrow pore-size distribution of 2.86 nm. The scanning electron microscopic (SEM) images also show the truncated octahedral shape and well-ordered pore system of MCM-48 particles.     

One-step preparation of thiol-modified mesoporous silica spheres with various functionalization levels and different pore structures

A wide range of mercaptopropyl-functionalized silica spherical particles of MCM-41 and MCM-48 (M41S family) have been prepared by co-condensation of mercaptopropyl trimethoxysilane (MPTMS) or mercaptopropyl triethoxysilane (MPTES) and tetraethoxysilane (TEOS) precursors in hydroalcoholic medium in the presence of a cationic surfactant as templating agent and ammonia as catalyst. It was possible to control the mesostructure type (hexagonal or cubic) by monitoring the water-to-ethanol ratio and the type of organoalkoxysilane precursor employed. Materials displaying various functionalization levels were obtained by varying the MPTMS or MPTES contents from 3 to 50% in the co-condensation synthesis medium. This gave rise to a wide range of porous solids with approximately the same particle size and morphology but featuring different functionalization levels and various degrees of structural order. They were characterized by X-ray diffraction (XRD), N₂ adsorption-desorption isotherms and BET analysis, scanning and transmission electron microscopy, ²⁹Si and ¹³C solid state nuclear magnetic resonance (NMR), particle size distribution measurements, and elemental chemical analysis. Mercaptopropyl groups were readily incorporated with high yields (>90%) by the co-condensation route. All samples exhibited spherical morphology with similar particle size but both the level of ordering and porosity of solids obtained by co-condensation were found to decrease when increasing the amount of organo-functional groups.     

CMC和CTAB双模板法合成具有稳定结构的MCM-41中孔分子筛

以羧甲基纤维素和十六烷基三甲基溴化铵为双模板,制备出了具有更高稳定性并且具有高度有序二维六方结构的MCM-41介孔分子筛.透射电镜和X射线衍射结果表明,以双模板制备的MCM-41介孔分子筛具有高度有序的二维六方(p6mm)孔道结构.此外,以双模板制备的MCM-41介孔分子筛焙烧前后的X射线衍射结果表明,在焙烧过程中其晶胞收缩比例为3.1%.与以纯表面活性剂为模版制备的MCM-41介孔分子筛(晶胞收缩比例为9.7%)相比,双模板制备的MCM-41介孔分子筛具有更高的稳定性能. MCM-41介孔分子筛稳定性能的提高可能是由于在硅物种、表面活性剂以及羧甲基纤维素在自组装过程中,羧甲基纤维素表面丰富的羟基与硅物种Si-(OH)x的相互作用促进了Si-(OH)x的缩聚.     

One pot synthesis of ordered mesoporous organosilica particles bearing propyl-, octyl- and hexadecyl-chains

New hybrid organic–inorganic materials exhibiting ordered mesoporous structures have been synthesized by co-condensation of tetraethoxysilane and various alkyltrimethoxysilanes with increasing length of the hydrocarbon chain (propyl, octyl, hexadecyl), in water–ethanol solution containing ammonia, in the presence of a cationic surfactant (cetyltrimethylammonium bromide) as templating agent. The obtained hybrid materials were characterized by using several physico-chemical techniques, such as X-ray diffraction, N₂ adsorption, ²⁹Si MAS NMR, SEM and elemental analysis. It was shown that the direct synthesis procedure allows obtaining ordered hybrid mesoporous silica with various contents of organic functions, from 5 to 20 %. Moreover, increasing the chain length of the organic group, from propyl to octyl and hexadecyl leads to a change of the pore structure from hexagonal p6mm MCM-41 type architecture to cubic Ia3d MCM-48 type mesostructure.     

不同结构颗粒对PMMA基复合材料性能影响

采用原位本体聚合法制备PMMA/MCM-41(with template),PMMA/SBA-15(with template),PMMA/SiO2三种复合材料.研究了介孔分子筛MCM-41,SBA-15和SiO2对PMMA复合材料拉伸强度,冲击强度,热稳定性的影响.由于合成介孔分子筛MCM-41,SBA-15时所用的模板剂CTAB和P123分布于孔口处和颗粒表面上,分别与PMMA基体产生物理缠结作用,增加了两者的相容性;且P123(EO20PO70EO20)表面有较大的PO/EO比率,与小分子量的CTAB相比有较强的疏水性,使得PMMA/SBA-15(with template)复合材料的性能要优于PMMA/MCM-41(with template).     

Surface modification to improve the sorption property of U(VI) on mesoporous silica

Polyoxometalates K₇[α-PW₁₁O₃₉]·14H₂O (PW11) modified mesoporous silica (MCM-48) with cubic structure, was prepared by impregnation and calcination methods. The modified mesoporous silica sorbent (PW11/MCM-48) was studied as a potential adsorbent for U(VI) from aqueous solutions. MCM-48 and PW11/MCM-48 were confirmed by X-ray diffraction and nitrogen physisorption techniques. The results indicate the original keggin structure of PW11 and mesoporous structure of MCM-48 are maintained after supporting PW11 on mesoporous silica MCM-48. The effects of contact time, solid-to-liquid ratio (m/V), solution pH and ionic strength on U(VI) sorption behaviors of the pure and modified mesoporous silicas were also studied. Typical sorption isotherms such as Langmuir and Freundlich isotherms were determined for sorption process. The results suggest that the sorption of U(VI) on MCM-48 or PW11/MCM-48 are strongly dependent on pH values but independent of ionic strength. The sorption capacity of PW11/MCM-48 for U(VI) is about ten times more than that of MCM-48.     

MCM-48介孔分子筛的高压合成

采用正硅酸乙酯（TEOS）作硅源,十六烷基三甲基溴化铵（CTAB）为模板剂,在高压 （约7 MPa）和373 K下合成了MCM-48介孔分子筛.用XRD、氮气吸附及29Si MAS NMR对样品 进行了表征.与常压合成的相比,高压下合成的MCM-48具有更高的热稳定性和水热稳定性.2 9Si MAS NMR结果表明,高压有利于分子筛孔壁的聚合,导致分子筛结构更加完善,从而使 其具有更高的稳定性.     

Electrodeposition of mesoporous V2O5 with enhanced lithium-ion intercalation property

Mesoporous vanadium oxide (V₂O₅) thin films were deposited electrochemically onto indium tin oxide-coated glass substrates from an aqueous solution of vanadyl sulfate using CTAB (hexadecyltrimethylammonium bromide) as a templating agent. For comparison, a control sample was electrodeposited without CTAB templating. Transmission electron microscopy and small angle X-ray diffraction indicated the presence of mesoporosity with a well-ordered lamellar phase in the electrodeposited films. The crystallinity of the V₂O₅ thin films was confirmed by X-ray diffraction. Cyclicvoltammetry and chronoamperometry were used to measure electrochemical properties of synthesized films. The mesoporous films prepared with CTAB templating had a much higher capacity and lithium-ion diffusion rate than the non-porous electrode prepared without CTAB templating.     

纯硅MCM-48的合成研究

以正硅酸乙酯为硅源,非离子型表面活性剂聚乙二醇辛基苯基醚和阳离子型表面活性剂十六烷基三甲基溴化铵为共模板水热法合成了纯硅MCM-48分子筛。利用范德华力和氢键,聚乙二醇辛基苯基醚不仅可降低合成MCM-48所需阳离子表面活性剂的用量,而且有利于制备有序性好和稳定性高的MCM-48;并与单一阳离子表面活性剂制备的MCM-48的稳定性进行比较。     

MCM-48介孔材料相转化合成的形成机制

利用水热合成的方法,使用新型的表面活性剂十六烷基三甲基对苯磺酸盐作为模板剂合成了高质量的MCM-48介孔分子筛,并用X-射线衍射(XRD)、扫描电镜(SEM)、高分辨透射电镜(HRTEM)以及N₂吸附-脱附进行了表征。合成过程的研究表明该合成体系经历了三相,起始相为具有六方对称性的MCM-41,随着加热时间的延长,生成了具有立方对称性的MCM-48,进一步延长加热时间则生成了层状相MCM-50。三相转变发生的核心驱动力来自于表面活性剂有效堆积参数g因子的改变。另外,XRD、傅立叶变换的红外光谱(FT-IR)以及固体魔角自旋核磁共振(²⁹Si MAS NMR)的表征结果证明：随着晶化时间的延长,相转变的同时伴随着介孔材料的孔壁逐渐由原子无序的非晶态向原子有序的晶态结构转变。最终形成的原子有序层状介孔分子筛可以作为扩孔型微孔分子筛合成的有效前驱体。     

介孔Ce-MCM-48的合成及其可见光催化性能研究

分别利用十六烷基三甲基溴化铵(CTAB)、正硅酸乙酯(TEOS)为模板剂和硅源,合成了高度有序的MCM-48材料。通过浸渍法制备了Ce含量不同的MCM-48(Ce-MCM-48s)材料。采用TG-DTA、小角XRD、N2吸-脱附、FT-IR、TEM、XPS和UV-vis等对Ce-MCM-48s进行了表征。XRD、N2吸-脱附和TEM证明Ce-MCM-48s具有与MCM-48相似的三维螺旋立体结构;FT-IR和XPS表明MCM-48孔道及其表面已被Ce氧化物所覆盖。可见光催化降解罗丹明B的实验证明,10%Ce-MCM-48的催化降解效率好于纯CeO2,商用TiO2(P125),5%Ce-MCM-48和15%Ce-MCM-48的。     

含氟体系中合成高品质的MCM-48介孔分子筛

在含氟体系中以正硅酸乙酯和十六烷基溴化铵作为硅源和模板剂,合成高质量的MCM-48。主要考察了各种影响合成MCM-48的因素,得到的产物分别用XRD,TEM和N₂吸附-脱附技术进行表征。结果表明,合成高质量MCM-48的条件是温度为393 K,时间为24 h,CTAB/Si比为0.65;得到的MCM-48具有较大的比表面积(130 5 m²/g),孔径分布比较集中(2.416 nm)。     

Hemicyanine dye as a surfactant for the synthesis of bicontinuous cubic mesostructured silica

In this paper, we developed a facile way to synthesize highly ordered optically active MCM-48 at room temperature, by using mixtures of hemicyanine dye N-alkyl-2-[p-(N,N-diethylamino)-o-(alkyloxy)]pyridinium bromide (denoted as o-CnPOCm, Scheme 1) and cetyltrimethylammonium bromide (CTAB) as the structure-directing agents. The mesoporous materials were systematically characterized by powder X-ray diffraction, transmission electron microscopy, nitrogen sorption, and thermogravimetry. The resultant MCM-48 exhibits unusually high thermal stability. For example, in the case of o-C(2)POC(14), it can retain its cubic structure even under calcinations at 900 degrees C for 5 h, although the pore size is shifted to the micropore region because of shrinkage of the framework. The typical surface area and pore volume are 980 m(2)/g and 0.44 cm(3)/g, respectively, for the powder calcined under such a high temperature. This is the first report of room-temperature synthesis of MCM-48 with such good thermal stability using cationic-cationic mixed surfactant as the structure-directing agent. The fluorescence lifetimes of the as-synthesized mesostructured MCM-48 were also measured, and the result showed that the incorporated dye molecules have a 1 order of magnitude longer lifetime than that of free species in solution, showing that the hemicyanine dye molecules are well dispersed within the CTAB surfactant matrix. Furthermore, we compared eight other dye congeners (Scheme 1) to fully investigate the mesophase resulting from the dye-CTAB system. The results show that, upon addition of the dye surfactant to the starting mixtures, the mesostructured silica undergoes an intrinsic phase-transition process; however, specific dye geometry is required to obtain MCM-48 at room temperature. Those functionalities as well as the designed synthesis of this novel mesostructured MCM-48 material promise a bright future in multifunctional optical and electric nano- and microdevices (e.g., waveguides, laser, light-emitting diodes, etc.) and also shed light on the self-assembly behavior in complex colloidal system.     

Preparation of H-mordenite/MCM-48 composite and its catalytic performance in the alkylation of toluene with <Emphasis Type="Italic">tert</Emphasis>-butanol

A series of HM/MCM-48 samples with different SiO₂/Al₂O₃ molar ratio were prepared by sol-gel method. The prepared catalysts were characterized by XRD, N₂ adsorption-desorption, NH₃-TPD, FT-IR, SEM, and TEM techniques, and their catalytic performance was investigated in alkylation of toluene with tert-butanol. The adsorption capacity and the acid sites amount of HM/MCM-48-4 sample prepared by growing MCM-48 on the surface of HM zeolite are much higher than that of their mechanical mixture (HM/MCM-48(4) sample) due to its biporous structure; it shows higher catalytic performance than other HM/MCM-48 samples. The influence of reaction conditions on the catalytic performance of HM/MCM-48-4 zeolite was discussed. Toluene conversion of 41.4% and p-tert-butyltoluene selectivity of 73.5% were obtained at the weight ratio of toluene to HM/MCM-48-4 of 5, reaction temperature of 453 K, reaction time of 5 h and the molar ratio of toluene to tert-butanol of 0.5.     

基于长链离子液体模板合成Fe(Co、Ni)-MCM-48

以两亲长链离子液体(氯化-1-十六烷基-3-甲基咪唑)为模板剂,采用水热合成方法,分别合成了含铁、钴和镍的立方介孔分子筛MCM-48。通过XRD、TEM、ICP-AES、FTIR、UV-Vis和N₂吸附/脱附实验对其结构和形态进行了表征,并考察了钴掺杂量和模板剂用量对合成立方相结构的影响。结果表明,用该方法合成的试样具有较高的比表面积和规则的立方介孔孔道结构等特征;相对于铁和镍的掺杂试样,钴物种能以四面体的结构稳定地存在于立方介孔分子筛骨架中。     

MCM-48介孔材料相转化合成的形成机制

利用水热合成的方法,使用新型的表面活性剂十六烷基三甲基对苯磺酸盐作为模板剂合成了高质量的MCM-48介孔分子筛,并用X-射线衍射(XRD)、扫描电镜(SEM)、高分辨透射电镜(HRTEM)以及N₂吸附-脱附进行了表征。合成过程的研究表明该合成体系经历了三相,起始相为具有六方对称性的MCM-41,随着加热时间的延长,生成了具有立方对称性的MCM-48,进一步延长加热时间则生成了层状相MCM-50。三相转变发生的核心驱动力来自于表面活性剂有效堆积参数g因子的改变,随着反应时间的延长,由于对甲基苯磺酸根离子（Tos^-）的流失,表面活性剂极性头所占的有效面积（a₀）明显减小,g值变大。另外,XRD、傅立叶变换的红外光谱(FT-IR)以及固体魔角自旋核磁共振(²⁹Si MAS NMR)的表征结果证明：随着晶化时间的延长,相转变的同时伴随着介孔材料的孔壁逐渐由原子无序的非晶态向原子有序的晶态结构转变。最终形成的原子有序层状介孔分子筛可以作为扩孔型微孔分子筛合成的有效前驱体。