HYDROXYLATION OF PHENOL BY IRON(Ⅱ)-PHENANTHROLINE(PHEN)/MCM-41 ZEOLITE

MCM-41 zeolite and Iron (Ⅱ) -Phen/MCM-41 zeolite have been preparedand characterized by XRD,IR, NH3-TPD, BET and UV-Vis. The Iron(Ⅱ)-Phen/MCM-41 zeolite+30% H2O2 system is capable for catalyzing hydroxylation of Phenol.

Exploring suitable ZSM-5/MCM-41 zeolites for catalytic cracking of n-dodecane: Effect of initial particle size and Si/Al ratio

In this study,various ZSM-5/MCM-41 micro/mesoporous zeolite composites have been prepared by alkalidesilication and surfactant-directed recrystallization of ZSM-5.The effects of particle size and Si/Al ratio of initial ZSM-5 zeolites on the structure and catalytic performance of ZSM-5/MCM-41 composites are studied.The results of XRD,TEM N_2-adsorption-desorption,NH_3-TPD and in situ FT-IR revealed that ordered hexagonal MCM-41 mesopores with 3-4 nm pore size were formed around ZSM-5 crystals,and the specific surface area and mesopore volume of composites increased with increasing the Si/Al ratio of initial ZSM-5.Catalytic cracking of n-dodecane(550℃,4 MPa) showed that the ZSM-5/MCM-41 composites obtained from the high Si/Al ratio and nano-sized initial ZSM-5 zeolites exhibited superior catalytic performance,with the improvement higher than 87%in the catalytic activities and 21%in the deactivation rate compared with untreated zeolites.This could be ascribed to their suitable pore structure,which enhanced the diffusion of reactant molecules in pores of catalysts.

Synthesis and Characterization of Mesoporous Materials MCM-41 Incorporated by Yttrium, Neodymium and Samarium

Using cetyl-trimethyl-ammonium bromide （CTMAB） as template and tetraethylortho-silicate （TEOS） as silica source, the MCM-41 mesoporous materials incorporated in framework by Y, Nd and Sm were synthesized by hydrothermal synthesis method. The structure, morphology of materials and the state of Y, Nd, Sm in materials were investigated by means of XRD, nitrogen adsorption-desorption, SEM, IR spectrometry, TG-DTA. The XRD results indicate that the samples possess the mesoporous MCM-41 structures with ordered hexagonal arrangements. Y, Nd and Sm ions can get into the framework of mesoporous materials. Nitrogen adsorption desorption isotherms show that the samples have typical mesopores characteristics. SEM micrographs reveal that incorporated sampies show a spherical morphology and the diameters are averagely 0. l0 to 0.15 μm. In IR spectrum of samples, there are the feature adsorption peaks about Si-O-Ln（Ln=Y, Sm, Nd）at 960-985 cm^-1, which affirm that Y, Nd, Sm ions locate in the framework of several mesoporous materials. Results from TG-DTA analysis suggest that two different template sorption sites exist in the framework of YMCM-41, SmMCM-41, NdMCM-41, which powerfully proves that the presence of Y, Nd and Sm in Si framework of the materials.

Thin Film of Mesoporous MCM-41 Grown on Indium-Tin-Oxide Glass Substrate

From a basic solution containing celyltrimethylammonium cations as the template, thin film of mesoporous MCM-41 has been grown on the surface of a pre-treated indium-tin-oxide conducting glass substrate. The channel axis of the film is oriented parallel with the surface plane of the substrate, and the film is stable after careful removal of template in vacuum.

Synthesis and Characterization of Mesoporous Silicon Oxynitride MCM-41 with High Nitrogen Content

Mesoporous silicon oxynitrides MCM-41 were synthesized successfully. The resulting materials not only have high nitrogen contents and good structural characteristics of MCM-41 (high surface area, narrow pore size distribution and good order), but also are amorphous. The composition and structure of the materials were investigated by CNH element analysis, XPS, Si MAS NMR, XRD, HRTEM and N-2 sorption, respectively. Mesoporous silicon oxynitrides MCM-41 with a high nitrogen content are still non-crystal (amorphous).

Removal of Fluoride from Water Using Mesoporous MCM-41: An Optimization Approach Using Response Surface Methodology (RSM)

Fluoride above 1.5 mg·L-1 is injurious to health. Removal of fluoride from water using mesoporous MCM-41 as a strong adsorbent material has been attempted. Characterization using transmission electron microscopic study of calcined MCM-41 showed the regular hexagonal array of mesoporous channels with an average size of 20 nm and the surface area (BET study) of 1306.96 m2·g-1. The average pore size of the particles was found to be 14.21 nm. A study on the effect of contact time on the removal of fluoride revealed that more than 85% uptake of fluoride onto MCM-41 was achieved at a contact time of 120 min. From the Langmuir adsorption study, the maximum sorption capacity of fluoride was found to be 63.05 mg/g at 301 K. From the thermodynamic study, the +ΔHo value of 2.29 kJ·mol-1 indicated the endothermic nature of the removal process. Application of Response Surface Model suggested that 77.88% of fluoride removal can be achieved at fluoride concentration of 10 mg·L-1, pH (6.3), and contact time of 120 min.

Synthesis and Characterization of Mesoporous Materials MCM-41 Incorporated by Yttrium, Neodymium and Samarium

Using cetyl-trimethyl-ammonium bromide （CTMAB） as template agent and tetraethylorthosilicate （TEOS） as silica Source, the MCM-41 mesoporous materials were synthesized with Y, Nd and Sm incorporated in the framework under hydrothermal conditions. The structure and the micro-morphology of the materials and the state of Y, Nd and Sm were investigated through the analyses of XRD, nitrogen adsorption-desorption isotherm, SEM, IR and TG-DTA. The XRD resuits indicate that the synthetic samples are of typical structure of mesoporous MCM-41 with ordered hexagonal arrangements, and Y, Nd and Sm can be incorporated into the framework of these mesoporous materials. Nitrogen adsorption-desorption isotherms show that the samples possess the typical mesopores character. SEM micrographs reveal that the incorporated samples show a well-defined spherical morphology with the diameter ranging 0.10 - 0.15μm. The occurrence of two different template sorption sites in the framework as revealed by TG-DTA analysis further suggests the presence of Y, Nd and Sm in siliceous framework.

Large Pore Mesoporous MCM-41 Templated from Cetyltriethylammonium Bromide

Following hydrothermal synthesis process, MCM-41 was synthesized by using cetyltriethylammonium bromide as templating agent. The experimental results showed that MCM-41 with pore diameter in the range of 4-7 nm can be obtained by adjusting nsurf/nsi. It was proved that cetyltriethylammonium bromide is an effective templating agent for increasing pore diameter of molecular sieve MCM-41.

Synthesis of Mesoporous Molecular Sieve MCM-41 in Extremely Dense System

Mesoporous molecular sieve MCM-41 has been synthesized in the extremely dense system (with H2O/Si<10) and characterized by XRD, N-2 adsorption isotherm as well as probe reactions of cracking of cumene and isomerization of o-xylene.

Simultaneous Removal of Surfactant Template from MCM-41 and Implantation of Transition Metal Complexes into Mesopores with Supercritical Fluid

The simultaneous removal of up to 92% of the surfactant template and chemical implantation of transition metal complexes into mesopores has been successfully achieved by treating as-synthesized pure siliceous MCM-41 with supercritical CO2 modified with CH2Cl2/MeOH mixture, resulting in the formation of functionalized material with uniform pore structure.

双组元Y/MCM-41中微孔复合分子筛的合成和表征

通过原位处理分步晶化、水热合成的方法 ,首次从NaY凝胶出发制备了含有Y和MCM 41两种分子筛成分的Y/MCM 41中微孔复合分子筛新材料 ,考察了合成条件对复合分子筛晶化的影响 .利用层厚法和相对结晶度工作曲线法确定了复合材料中两种分子筛的相对含量 .通过XRD ,MASNMR ,SEM ,XPS ,IR ,N2 吸附脱附、热处理等手段对复合材料进行了表征 ,并与MCM 41和Y型分子筛的有关性能进行了对比研究 .结果表明 ,复合分子筛材料的热和水热稳定性高于相同分子筛比例的机械混合样品 .与机械混合物样品相比 ,其中孔表现出孔径缩小、孔道规整性变差、孔壁增厚和部分结晶化的特点 ,复合材料中两种分子筛之间存在界面效应 ,推测Y/MCM 41复合分子筛材料具有“包覆式”结构特征 .以模型化合物1,3 ,5 三异丙基苯为进料考察了其催化裂化活性 。

强酸性和水热稳定的MCM-41分子筛的合成

以ZSM 5沸石分子筛为原始硅铝源,在碱性条件下,通过水热法合成出了孔壁含有ZSM 5预结构单元的MCM 41介孔分子筛。采用XRD、N2 吸附脱附、FT IR和NH3 TPD等表征手段对样品进行分析,结果表明该分子筛是含有ZSM 5 沸石预结构单元的六方晶相结构,该介孔分子筛的孔壁明显厚于常规方法合成的MCM 41,具有较高的水热稳定性和较强的酸性。

高表面积MCM-41的合成与性能

通过易于控制的手段,合成出了超高表面积的MCM-41分子筛,并采用XRD、N2吸附脱附、热重-差热分析、SEM等测试手段对合成样品进行分析表征,主要考察了晶化时间对分子筛表面积的影响.其XRD结果表明,合成的固体产物具有六方排列的孔道结构,结晶度高.氮吸附脱附实验表明,产物具有单一的孔径分布,其BET表面积可达1300m2·g-1左右,合成样品的平均孔径约3.2nm,适宜的晶化时间是50～100h.热重分析表明,样品热稳定性好,吡啶升温脱附曲线表明合成的样品具有弱酸性.

ZrO_2/Ti-MCM-41催化聚丙烯裂解反应的研究

采用水热合成法制备了中孔分子筛ZrO2/Ti-MCM-41,通过XRD和N2吸附-脱附对其进行表征。结果表明,该分子筛具有中孔结构,并且随着ZrO2含量的增加,ZrO2/Ti-MCM-41孔道的长程有序性和结晶度有所减弱,直至失去中孔结构。将其应用于聚丙烯(PP)催化裂解反应,通过考察负载量、反应温度、催化剂用量和反应时间,对ZrO2/Ti-MCM-41催化裂解PP反应的规律进行了研究。结果表明,负载ZrO2质量分数为18%的ZrO2/Ti-MCM-41,在反应温度400℃、m(ZrO2/Ti-MCM-41)∶m(PP)=0.02和反应时间30 min条件下,PP转化率可达91.2%,液体产物收率为83.6%,优于热裂解及传统的HZSM-5小孔分子筛催化剂的催化裂解结果。

MCM-41型中孔分子筛的应用

介绍了MCM-41型中孔分子筛的性能、合成过程和近年来在催化、吸附、纳米、光学材料和环保等领域的应用情况,并对MCM-41的发展前景进行了展望。

提高MCM-41分子筛稳定性的研究

采用ＸＲＤ、ＩＲ、ＴＥＭ及自动吸附仪分析了常规ＭＣＭ－４１硅铝分子筛的热与水热稳定性差的原因，并采取增加超大孔分子筛孔壁厚度的措施，合成出了结构稳定性良好的ＭＣＭ－４１分子筛，同时考察了影响ＭＣＭ－４１分子筛孔壁厚度的因素。结果表明，适当降低反应体系的ｐＨ值，向体系中加入适量电解质能有效地提高ＭＣＭ－４１分子筛孔壁厚度。壁厚２．７ｎｍ的ＭＣＭ－４１分子筛在８００℃水蒸汽处理２ｈ后，ＸＲＤ峰强度保留率为５５％，从而使ＭＣＭ－４１分子筛的水热稳定性提高到一个新的高度。

SO_4^(2-)/TiO_2-Al-MCM-41制备及其催化合成戊酸丁酯

选择硅酸四乙酯为硅源,在室温和pH=3.5条件下合成具有较低硅铝比的MCM-41型分子筛。以其为基础载体,采用浸渍和焙烧法制备含钛分子筛型固体超强酸。低温N2吸附、IR、SEM和XRD分析表明,铝已进入分子筛的骨架中;Hammett指示剂测定表明,酸强度H0<-14.52。以戊酸丁酯合成为探针反应,考察了催化剂的催化性能。结果表明,反应温度为138℃、催化剂用量为反应物总质量的1%、丁醇和戊酸的物质的量比为3∶1条件下,产品转化率达98.5%。

MCM-41 Prepared with Ionic Liquid and Cethytrimethylammonium Bromide as Co-templates

The mesoporous molecular sieves MCM-41 were prepared using room tempera-ture ionic liquid （RTIL） synthesized in laboratory and cethytrimethylammonium bromide （CTAB） as compound templates for the first time. They were prepared under low aging temperature and short aging time. Via characterizing by XRD and nitrogen adsorption instrument, MCM-41 synthesized by this new method exhibited good crystal structure and narrow pore distribution. The following pre-paratory conditions was optimal： the molar ratio of RTIL to CTAB was 1.0∶1.0, aging at 80 ℃, for 40 h and calcined at 540 ℃. It is found that the acidified MCM-41 improves its activity as catalyst over the unmodified ones.

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。

Preparation,Characterization and Catalytic Activity of Palladium Nanoparticles Embedded in the Mesoporous Silica Matrices

Novel in-situ reduction approach was applied for the synthesis of palladium nanoparticles in the pores of mesoporous silica materials with grafted siliconhydride groups. Matrices possessing different structural properties (MCM-41, SBA-15 and Silochrom) were used. Samples were studied by nitrogen adsorption-desorption method, low-angle X-ray diffraction, transmission electron microscopy (TEM) and FT-IR/PAS spectroscopy. The temperature-programmed oxidation (TPO) and reduction (TPR) methods were applied to examine reducibility of palladium species. Palladium containing catalysts were tested in methane oxidation reaction. It was demonstrated that relatively large pores in SBA-15 type silica facilitated formation of well-dispersed palladium nanoparticles confined in the pores channels. In the case of MCM-41 support, metallic palladium nanoparticles were formed on the external surface. The obtained materials showed high catalytic activity. Lower activity of the samples containing small crystallites located in the pore volume at high temperatures was related to worse accessibility of active sites to the reation mixture.