表面活性剂对纳米MCM-41分子筛分散性的影响

采用聚乙二醇为分散剂,十六烷基三甲基溴化铵为模板剂,正硅酸乙酯为硅源,在室温碱性条件下合成了粒径为40～60 nm的单分散纳米球形MCM-41分子筛.利用XRD、TEM和N2吸附脱附等手段研究了聚乙二醇用量对纳米球形MCM-41的分散性和介孔结构的影响.结果表明,表面活性剂PEG的加入,可以明显改善纳米颗粒的分散性并且对颗粒形貌影响不大;表面活性剂PEG的加入,样品的六方结构有序性和孔尺寸发生变化.PEG量在1%～20%范围内,样品仍具有较高的六方孔道有序性;PEG量过大(60%)有序性明显下降.随着PEG加入量的增加,纳米MCM-41的晶面间距增大,孔尺寸增大.适量的聚乙二醇可以得到有序性好、比表面积大、孔径均一和孔隙率大的单分散纳米球形MCM-41分子筛.     

室温下介孔分子筛MCM-41的合成与表征

在室温下 ,以十六烷基三甲基溴化铵 (CTABr)为模板剂 ,正硅酸乙酯和水玻璃为硅源 ,通过水热法分别合成出了性能优良的介孔分子筛MCM 4 1,并采用XRD、N2 吸附脱附、FTIR、SEM、热重等手段对合成的样品进行了分析表征。其结果表明 ,合成的固体产物具有MCM 4 1特有的六方排列的孔道结构 ,并且具有较高的有序度、比表面积、孔容和热稳定性     

杂原子MCM-41分子筛的合成和催化性能

采用水热合成法合成了金属原子(Zn,Ni,Fe,Al,Cu,Ce)掺杂的MCM-41介孔分子筛(简称T-MCM-41),并将其应用于邻苯二甲酸二(2-乙基已)酯(DOP)的合成反应,研究了不同原子的掺杂对T-McM-41的结构,比表面积和孔径、酸性及催化性能的影响.结果表明,所制备的T-McM-41仍然具有六方有序排列结构,比表匝f积较高(550-900 m2/g)、孔径大(3 nm左右),杂原子的引入使T-MCM-41产生了酸中心,从而使其对DOP的合成具有很好的催化活性和选择性.用T-MCM-41(T=Zn,Fe,Al,Cu)催化DOP的合成反应,在5 h的反应时间内苯酐的转化率可以达到95.5%以上,DOP的选择性可达到96.5%以上.T-MCM-41催化剂具有很好的稳定性,Al-MCM-41在重复使用5次后仍具有较好的催化活性.     

Influence of pH on the sorption behaviour of uranyl ions in mesoporous MCM-41 and MCM-48 molecular sieves

The sorption of uranyl ions in mesoporous MCM-41 and MCM-48 was accomplished with the help of a direct-template-exchange route, and the progress was monitored as a function of pH of the precursor uranyl nitrate solution. Under identical conditions of synthesis, around one and a half times larger amount of uranium was found to be sorbed in MCM-48 (∼12.5 wt.%) as compared to MCM-41 (∼9.5 wt.%). Further, the powder X-ray diffraction (XRD) data revealed that the expansion of unit cell parameters and broadening of reflections of the uranium containing samples depended on the pH of the precursor uranyl solution. Likewise, the Fourier transform infrared spectroscopy (FT-IR) studies showed a progressive decrease in the frequency of the axial OUO asymmetric stretching vibrational band, ν_a(UO) of the anchored uranyl groups with the increase of pH of the exchanging uranyl solution. The presence of two bands at ∼920 and 879 cm⁻¹ for uranyl exchanged samples prepared at pH > 5 indicated the presence of trinuclear (UO₂)₃⁺₅(OH) species. The occlusion of uranium thus depends upon the pore structure of the host material and the nature and dimension of the hydrolysis species formed at a particular pH of uranyl solution. Furthermore, the template-exchange of hexavalent uranium in MCM-41 and MCM-48 not only results in the formation of bulky hydrolysis species in the mesovoids, but also substitutes (isomorphously) in the silicate matrix resulting in the formation of UMCM-41 and UMCM-48.     

资源化利用铁尾矿制备全硅介孔分子筛MCM-41

以鞍山铁尾矿为硅源,CTAB为模板剂,采用水热合成法合成出全硅介孔分子筛MCM-41。采用X射线衍射分析研究了pH值、CTAB与SiO2配比、晶化温度和晶化时间对MCM-41结构的影响,结果表明MCM-41的合成条件为n（CTAB）/n（SiO2）=0.05～0.60,pH值=8～11,晶化时间〉24h,晶化温度60～100℃。TEM可观察到样品具有典型的按六方对称性排列的孔道结构,孔径在2～4nm变化。FT-IR证明了分子筛具有硅氧四面体骨架。     

Crystal morphology control of AlPO4-11 molecular sieves by microwave irradiation

AlPO₄-11 molecular sieves with morphologies of aggregated sphere, clump, faggot and rod were successfully synthesized by microwave irradiation using diisopropylamine as template. By adjusting the crystallization time, the morphology of the AlPO₄-11 molecular sieves changed from sphere to clump and then to faggot. With the increasing concentration of HF, the morphology of AlPO₄-11 molecular sieves changed from sphere to rod gradually, which exactly consisted with the variation of the XRD patterns. Slow nucleation rate caused by the chelated function of Al–F may be the main reason to direct the crystal growth on the special direction. Meanwhile, some control experiments including use of HCl and increasing the concentration of water also showed the same preferential growth of the crystals.     

不同偶联剂对介孔分子筛MCM-41的表面修饰及对MCM-41/环氧树脂性能的影响

使用2种硅烷偶联剂(KH550和KH792)对介孔分子筛MCM-41进行表面改性,采取氮气吸附-脱附、FTIR和TGA等进行表征,并采用原位聚合法制备了MCM-41/环氧树脂复合材料,研究了偶联剂种类和MCM-41用量等对复合材料固化过程及性能的影响。结果表明:硅烷偶联剂可与MCM-41表面的硅羟基反应,在分子筛内外表面接枝上功能化基团。经表面修饰的MCM-41比表面积下降为原来的1/5,KH550在MCM-41表面接枝率仅为KH792的一半。KH550与MCM-41外表面反应得更充分,KH792对MCM-41孔道内壁的修饰效果更强。固化动力学结果表明:KH792的功能化基团有伯胺和仲胺,与环氧树脂具有更高的反应活性,但不利于环氧大分子进入孔道,仅以球形粒子的形式添加在环氧树脂中;KH550表面修饰的MCM-41可使环氧大分子进入孔道内形成互穿结构。KH550表面修饰体系更多体现出MCM-41多孔的特征,形成了有机-无机互穿结构的复合体系,大幅度提高了储能模量和玻璃化转变温度。KH792表面修饰体系则呈常规球形纳米粒子的特征,其储能模量和玻璃化转变温度较纯环氧树脂有所提高但幅度不大。     

Characterization and investigation on the difference of hydrothermal stability for ordered mesoporous aluminosilicate sieves

Ordered hexagonal mesoporous aluminosilicates molecular sieves, designated as MSAMS-2A, MSAMS-2G and MSAMS-2, have been synthesized via re-crystallization of mesoporous SBA-15 within the diluted solution of aluminosilicate sol–gel, glycerol, and both of them, respectively. The three materials have been characterized by XRD, N₂ adsorption–desorption, FT-IR, FE-SEM, ²⁷Al MAS NMR and ²⁹Si MAS NMR, and the corresponding hydrothermal stability of these three sieves is in the order of MSAMS-2 > MSAMS-2G ? MSAMS-2A. The hydrothermal stability difference between MSAMS-2 and MSAMS-2G might be attributed to the synergistic effect of the higher condensation of silanol groups and insertion of all non-framework Al atoms into the framework of MSAMS-2. The hydrothermal stability of MSAMS-2G is higher than that of MSAMS-2A, which is likely because the high viscosity of glycerol will be in favor of the silanol groups interacting with zeolite-like subunits and moreover glycerol can act as a stabilizing guest molecule.     

Synthesis of MCM–41 mesoporous molecular sieves containing heteroatoms and their catalytic activity

采用水热合成法合成了金属原子(Zn, Ni, Fe, Al, Cu, Ce)掺杂的MCM--41介孔分子筛(简称T--MCM--41), 并将其应用于邻苯二甲酸二(2--乙基己)酯(DOP)的合成反应, 研究了不同原子的掺杂对T--MCM--41的结构、比表面积和孔径、酸性及催化性能的影响. 结果表明, 所制备的T--MCM--41仍然具有六方有序排列结构, 比表面积较高(550--900 m2/g)、孔径大(3 nm左右), 杂原子的引入使T--MCM--41产生了酸中心, 从而使其对DOP的合成具有很好的催化活性和选择性. 用T--MCM--41(T=Zn, Fe, Al, Cu)催化DOP的合成反应, 在5 h的反应时间内苯酐的转化率可以达到95.5%以上, DOP的选择性可达到96.5%以上. T--MCM--41催化剂具有很好的稳定性, Al--MCM--41在重复使用5次后仍具有较好的催化活性.     

Fe(III) containing MCM-48 type mesoporous molecular sieves with framework zeolite secondary building units

Fe(III) containing mesoporous materials (FeMMSH) with zeolite building units were first time synthesized. XRD and N2 adsorption/desorption analysis confirm the mesoporous characters similar to MCM-48. FT-IR analysis of FeMMSH showed an additional band at about 530-550 cm(-1), characteristic of double five-membered ring of zeolite (ZSM-5) secondary building unit. The Fe(III) in FeMMSH materials is present in tetrahedral, and distorted tetrahedral framework are evident from EPR and DRUV-VIS spectra.     

Dielectric spectroscopy of nano BaTiO3 confined in MCM-41 mesoporous molecular sieve materials.

Dielectric properties of barium titanate (BaTiO3) particles, synthesized directly in the pores of MCM-41 materials, have been investigated in the frequency range from 20 Hz to 1 MHz for temperature intervals from 100 K to 500 K. The dielectric spectra of BaTiO3 confined in these molecular sieves were compared with the results obtained from the investigation of pure MCM-41 materials. Obtained results confirmed successful incorporation of BaTiO3 into porous matrix, but no phase transition from paraelectric to ferroelectric phase was observed due to the particle size being smaller than the critical size. Also, the overall dielectric response of investigated materials is strongly influenced by adsorbed water molecules.     

聚乙烯亚胺修饰的介孔材料对CO2的吸附性能

在MCM-41上负载修饰剂-聚乙烯亚胺(PEI),采用氮吸附、红外光谱和热重(TG)等手段表征材料的结构,利用静态吸附的手段测定其对二氧化碳的吸附性能.结果表明,PEI改性后的MCM-41材料对二氧化碳的吸附性能有了明显改善.MCM-41分子筛吸附量由改性前的8.8 mg/g增加到了改性后的90.2 mg/g.此吸附剂...     

Extremely high surface area of ordered mesoporous MCM-41 by atrane route

Silatrane synthesized from inexpensive oxide precursor, silica and TEA was used as the precursor for MCM-41 synthesis at low temperature because of its stability in aqueous solutions. Using cationic surfactant hexadecyltrimethyl ammonium bromide (CTAB) as a template, the resulting meso-structure mimics the liquid crystal phase. Varying the surfactant concentration, ion concentration and temperature of the system, changes the structure of the liquid crystal phase, resulting in different pore structures and surface area. After heat treatment, very high surface area mesoporous silica was obtained and characterized using XRD, BET and TEM. XRD and TEM results show a clear picture of hexagonal structure. The surface area is extraordinarily high, up to more than 2400 m² g⁻¹ at a pore volume of 1.29 cm³ g⁻¹. However, the pore volume is up to 1.72 cm³ g⁻¹ when the surface area is greater than 2100 m² g⁻¹.     

介孔分子筛MCM-41的制备及其对Cr6+的吸附

以鞍山铁尾矿为硅源,CTAB为模板剂,采用水热法合成出介孔分子筛MCM-41。采用XRD、BET、HRTEM对样品进行了表征。将该介孔分子筛MCM-41应用于水中Cr6+离子的吸附,研究了吸附时间、吸附剂用量、初始浓度对分子筛吸附性能的影响,并探讨了吸附过程的表观吸附动力学模型及吸附等温模型。结果表明,增加吸附时间、吸附剂用量、初始浓度有利于分子筛对Cr6+离子的吸附。Cr6+的吸附过程遵循二级表观吸附动力学模型;在吸附剂表面的吸附遵循Langmuir吸附等温线模型。     

Fabrication of mesoporous carbonated hydroxyapatite/carbon nanotube composite coatings by microwave irradiation method

Carbonated hydroxyapatite/carbon nanotube composite coatings (MHCs) with mesoporous structures were fabricated by electrophoretic deposition of nacre powders and carbon nanotubes on Ti6Al4V substrates followed by treatment with a phosphate buffer solution (PBS) by microwave irradiation method. The carbon nanotubes are dispersed uniformly on the whole MHCs. The conversion mechanism of the crack-free nacre/carbonate nanotube composite coatings (NCCs) to MHCs is a dissolution-precipitation reaction. After soaking in PBS, calcium ions are released from the nacre powders and react with phosphate ions to form carbonated hydroxyapatite nanoparticles. These nanoparticles aggregate to form mesopores with the pore sizes of ~ 3.9 nm among them. Simulated body fluid (SBF) immersion tests reveal that MHCs have a good in vitro bioactivity.     

MCM-41的微波合成与比较

采用微波法合成出MCM-41介孔材料,并与水热法、室温法进行比较.结果表明:在120W微波功率下加热40min就可得到结构较理想的MCM-41介孔材料,且微波加热时间的变化会影响到样品的有序性,但对孔径影响不大.通过与水热法和室温法进行比较发现,微波法合成的MCM-41煅烧后的收缩率与水热法相近,比室温合成的MCM-41要小,因而其热稳定性比室温法好,与水热法差不多.     

Preparation of high nickel-containing MCM-41-type mesoporous silica via a modified direct synthesis method

A method with modifying tetraethyl orthosilicate (TEOS) with nickel species has been developed for the synthesis of mesoporous silica with high nickel content (11.8 wt.% of Ni or even higher). With the method, MCM-41-type materials were obtained with high BET surface area reaching 868 m²/g and pore volume up to 0.73 cm³/g. The materials were characterized by means of X-ray powder diffraction, transmission electron microscopy, energy dispersive X-ray spectroscopy, N₂ adsorption, Fourier transform infrared and X-ray photoelectron spectroscopy. Nickel species were incorporated into the silica frameworks. The mesostructures still remain after activation using H₂ at 773 K.