13X微孔沸石和MCM-41介孔材料的合成及用于处理含Cd2+废水

以天津蓟县钾长石矿粉为主要原料,经选矿、煅烧、水热处理等工艺成功合成了13X微孔沸石. 以气相氧化硅、氢氧化钠、十六烷基三甲基溴化铵等为主要原料,在水热条件下合成了MCM-41有序介孔材料. 采用XRD和N2吸附-脱附等手段对合成的13X沸石和MCM-41介孔材料的物相、比表面积、孔径、孔体积等进行了分析对比. 在此基础上,对13X沸石和MCM-41介孔材料处理含Cd2+废水的效果和机理进行了对比研究,确定了不同分子筛用量、不同初始pH值、不同混合时间下13X沸石和MCM-41介孔分子筛对水中Cd2+的吸附率和吸附量. 研究发现,尽管MCM-41的比表面积和孔径远大于13X沸石,但其对水中Cd2+的处理效果却低于13X沸石,这与13X沸石和MCM-41的孔道结构类型、化学组成、表面荷电性质等有关.     

MCM-41介孔材料的合成条件和特性对吸附镉离子的影响

以气相氧化硅为硅源,十六烷基三甲基溴化铵(cetyl trimethyl ammonium bromide,CTAB)为模板剂,分别在碱性[氢氧化钠(NaOH),四乙基氢氧化铵,tetraethyl ammonium hydroxide,(C2Hs)4NOH(TEAOH)]和酸性介质条件[盐酸(HCl)]T水热合成了MCM-41有序介孔材料MCM-41-N,MCM-41-T和MCM-41-H.用X射线衍射、氮气吸附-脱附等手段对比分析了合成的3种MCM-41介孔材料的物相、比表面积、孔径、孔体积等,发现酸性介质中合成的介孔材料的孔径最大.在此基础上,利用MCM-41介孔材料对比研究了处理含镉离子(Cd2 )废水的效果和机理,确定了不同介孔材料用量、不同初始pH值条件下MCM-41介孔材料对水中Cd2 的吸附率和吸附量.结果表明:介孔材料用量相同时,溶液pH值的增大有利于提高3种MCM-41介孔材料对水中Cd2 的处理效果.在pH值从7.0到8.0的过程中,其吸附率有1个突变,MCM-41-T的Cd2 吸附率从35.65%提高到62.15%;MCM-41-N的从38.80%提高到69.40%;MCM-41-H的从50.22%提高到73.47%.孔径最大的MCM-41-H对Cd2 的吸附效果最佳,最大吸附率为89.56%,最大吸附容量为8.57 mg/g.吸附溶液pH值的大小和介孔材料的孔径尺寸是决定吸附量大小的关键因素,因此,重点应通过优化合成工艺提高介孔材料的孔径.     

含锆介孔分子筛的微波合成与表征(英文)

在微波辐射条件下,以硅酸钠和硫酸锆为原料、十六烷基三甲基溴化铵为模板剂合成含锆介孔分子筛(zirconium-containing mesoporous molecular sieves,Zr-MCM-41).用X射线粉末衍射、红外光谱,透射电子显微镜、等离子发射光谱和比表面积孔径测定等测试手段表征经550℃焙烧后样品,同时研究锆添加量与分子筛比表面积及孔体积之间的关系.结果表明:利用微波技术合成Zr-MCM-41介孔分子筛,操作便利,节能省时,所得产物具有典型的MCM-41介孔分子筛结构,其比表面积为598.1～971.4m2/g,平均孔径大约为2.46～3A3nm.随着介孔分子筛中锆含量的增加,介孔分子筛的比表面积、孔体积变小,介孔有序性变差.     

由沸石纳米粒子自组装制备具有高催化活性中心和水热稳定的新型介孔分子筛材料

人们合成了一系列介孔分子筛材料,并发现它们在催化、吸附与分离以及化学组装制备先进材料和分子器件等方面具有很大的潜在应用价值.但是,介孔分子筛材料相对于微孔沸石分子筛存在着两个致命弱点:较低的水热稳定性和较不活泼的催化活性中心.这两个弱点大大地影响了介孔分子筛在催化反应中的广泛应用.本文系统地综述了最近几年利用沸石纳米粒子自组装制备具有高催化活性中心和水热稳定的介孔分子筛材料的研究进展.这包括利用硅铝沸石纳米粒子自组装制备具有强酸性和水热稳定的新型介孔硅铝分子筛材料,利用钛硅沸石纳米粒子自组装制备具有高催化氧化活性中心和水热稳定的新型钛硅介孔分子筛材料,以及利用含有不同杂原子的沸石纳米粒子自组装制备一系列水热稳定的新型介孔分子筛催化材料.     

软模板法合成介孔碳材料

介孔碳材料的比表面积很高,而且其拥有结构精细有序的纳米孔道,在多个工业领域有广阔应用前景。该文将主要讨论软模板法在介孔碳材料合成中的应用,对溶剂挥发诱导自组装法、水相合成法、宏观相分离法以及水热合成法进行详细分析,分别讨论四种方法的主要原理与合成介孔碳材料孔径的影响因素。所讨论的四种合成法是重要的介孔碳材料合成手段,有很强的应用价值。     

用脱镁海泡石制备介孔分子筛MCM-41

以脱镁海泡石为硅源,在水热条件下合成介孔分子筛MCM-41.考察了晶化时间、晶化温度、pH值等因素对介孔分子筛MCM-41的影响.用X射线衍射分析、Brumauer-Emmett-Teller法和红外分析表征MCM-41.结果表明:在pH值为12,晶化温度为100℃,晶化时间为24h时,所得MCM-41的结晶度最好,比表面积为860m2/g,孔体积为0.77 cm3/g,孔径为2.9nm,孔壁厚为1 nm.红外分析表明:脱镁海泡石在合成介孔分子筛MCM-41过程中生成了≡SiO-CTA 络合物.     

具有介孔结构丝光沸石的合成与表征

基于丝光沸石骨架结构固有的晶体缺陷特征,提出诱导晶体结构缺陷和由结构缺陷衍生晶内介孔的研究方案。采用三元有机超分子胶束模板剂和两段变温晶化水热法,制备出丝光沸石基多级介孔材料。通过粉末X射线衍射、77K氮吸附–脱附、场发射透射电子显微镜、氨程序升温脱附对合成的介孔材料的晶相、形貌、介孔特征和水热稳定性进行了表征。结果表明：所合成的典型丝光沸石具有较高的相对结晶度,介孔比表面积和介孔体积分别为152.7m2/g和0.163 cm3/g;晶体内介孔在3～50 nm区间呈多级分布;其酸性质与微孔丝光沸石相匹配;水热稳定性较有序介孔材料MCM-41有显著提高。与聚集态纳米沸石组装介孔材料不同,合成的介孔丝光沸石晶体表面上介孔排布密度和尺寸分布缺乏均一性,故而由体相结构缺陷诱导形成的附加介孔呈显著无序状态。     

MCM-41介孔分子筛的合成、改性及应用研究进展

介绍了MCM-41介孔分子筛的优点,主要表现在具有较大的比表面积,孔体积与孔径和可调变等。综述了MCM-41介孔分子筛的合成方法与改性研究现状,阐述了MCM-41介孔分子筛的应用研究进展。     

新型高水热稳定性MOR/MCM-41复合分子筛的合成

以丝光沸石分子筛为硅铝源,通过碱液处理和表面活性剂的自组装作用,水热条件下合成了MOR/MCM-41复合分子筛。通过XRD、SEM、TEM、N2吸附/脱附和水热稳定性处理等手段对合成的复合材料进行了表征。结果表明,复合材料不仅保留了原丝光沸石晶体的规则形貌,同时兼具微孔分子筛MOR和介孔分子筛MCM-41的特征,且介孔(20~30 nm)在微孔分子筛中较均匀地分布。水热处理测试结果表明,MOR/MCM-41复合分子筛具有较高的水热稳定性,水热处理100 h后介孔结构依然存在。     

MCM-41的孔径和添加量对环氧树脂力学性能的影响

以1,3,5三甲苯(TMB)为扩孔剂,水热合成了5种不同孔径(2.7～5.9 nm)的介孔二氧化硅MCM-41粉体,采用溶液共混法制备了MCM-41环氧树脂复合材料,研究了MCM-41孔径和添加质量对复合材料力学性能的影响。结果表明,添加1%最大孔径的MCM-41时,复合材料的力学性能达到最佳,拉伸强度、弯曲强度、弯曲模量分别比纯环氧树脂提高了54.6%、30.1%、68.3%。     

Characterisation and catalytic properties of MCM-41 and Pd/MCM-41 materials

Pure silica MCM-41 mesoporous molecular sieve material was synthesised and characterised by in situ synchrotron XRD, TEM, TGA/DTA and DRIFTS techniques. In situ energy dispersive XRD (EDXRD) confirmed the exact nature of the pore diameter of MCM-41 and the change in crystal structure on calcination. The IR band at 1057 cm^-1 of as-synthesised MCM-41 was shifted by 14 cm^-1 on heating to 673 K due to increased condensation of silanol groups to form Si-O-Si bridges. Calcined MCM-41 materials were used to support Pd, and the catalytic activities for 1-hexene and benzene selective hydrogenation were investigated. The Pd/MCM-41 catalyst showed high activity in hydrogenation of 1-hexene at an inlet reaction temperature of 298 K, but did not show any activity in hydrogenation for benzene. TEM results for the reduced Pd/MCM-41 catalysts revealed that the average Pd particle size was around 2-2.5 nm and these particles were located in the pores of MCM-41 and showed good distribution. TPR measurements showed that about 70% of palladium oxide (PdO) loading in the calcined catalysts was reduced at sub-ambient temperature. This revised version was published online in July 2006 with corrections to the Cover Date.     

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。     

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.     

MCM-41分子筛的合成

以十六烷基三甲基溴化铵(CTAB)为结构模板剂,正硅酸乙酯(TEOS)为硅源,正庚烷(MSDS)为辅助剂,合成出了MCM-41分子筛,并采用傅立叶变换红外光谱仪(FTIR)对分子筛结构进行了表征。探索了pH值、CTAB用量、MSDS用量、晶化温度和晶化时间对分子筛质量吸水率的影响。结果表明:反应体系pH值=10,n(CTAB)∶n(TEOS)=0.06,n(MSDS)∶n(CTAB)=4,晶化温度120℃,晶化时间24h为最佳合成条件。     

MCM-41 for furosemide dissolution improvement

The ordered mesoporous silica material MCM-41 was used to prepare a novel drug delivery system (DDS) for oral administration of the diuretic furosemide (FURO), labeled in class IV of the Biopharmaceutics Classification System (BCS). This drug is characterized by both low solubility and permeability and its absorption window is the stomach and the proximal small intestine. Thus, the aim of this work was the development of an immediate formulation that could improve the drug release in its preferential absorptive regions.Three inclusion products MCM-41-FURO-E/D, MCM-41-FURO-S and MCM-41-FURO-E have been prepared in three different ways in order to find the best preparation conditions. They were characterized by XRPD, DSC, FT-IR, TGA and B.E.T. and then the inclusion products displaying the best characteristics were submitted to in vitro studies. They evidenced that the examined inclusion products displayed FURO dissolution enhancement, followed by a complete release within 90 min. Moreover, physical stability studies revealed that MCM-41 is able to stabilize the drug preventing it from re-crystallization. At last, as FURO is light sensitive, the effect of MCM-41 on drug photochemical stability was also investigated and the results indicated the protective action exerted by the matrix.     

Toluene hydrogenation over nickel-containing MCM-41 and Ti-MCM-41 materials

Nickel-containing MCM-41 and Ti-MCM-41 mesoporous materials with different amounts of nickel were prepared by one-pot, sol–gel synthesis. The properties of the nickel catalysts were studied by means of X-ray diffraction (XRD), N₂ physisorption, UV-Vis spectroscopy and temperature programmed reduction (TPR) methods. The catalysts have been tested in the gas phase hydrogenation of toluene. The formation of various nickel species due to the different metal-support interaction was assumed for both of the supports. Strong metal–support interaction was supposed when Ti-MCM-41 was used as a support. It has been shown that the reducibility and the catalytic activity of the catalysts is strongly influenced by the host.     

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.     

Catalysis Over Pore-Expanded MCM-41 Mesoporous Materials

Pore-expanded MCM-41 (PE-MCM-41) silica was obtained via a two-step strategy consisting of synthesis of MCM-41 in the presence of cetyltrimethylammonium cations (CTMA⁺) followed by hydrothermal treatment in the presence of an aqueous suspension of dimethyldecylamine (DMDA). It is believed that the two surfactants self-organize into concentric cylinders comprised of an inverted DMDA micelle within a regular CTMA⁺ micelle. The amine head groups point towards the pore center, thus creating a hydrophilic channel within the pores. Selective extraction of DMDA afforded PE-MCM-41E, a highly porous material with hydrophobic surface. Calcination of as-synthesized PE-MCM-41 or PE-MCM-41E gave rise to PE-MCM-41C which exhibits a unique combination of large pores (up to 20 nm), large pore volume (up to 3.5 cm³/g) and large surface area, often exceeding 1000 m²/g. All three mesophases were used as starting materials for the development of innovative catalysts and adsorbents. Moreover, post-synthesis alumination of PE-MCM-41 and PE-MCM-41C led to novel large pore aluminosilicates with different Si/Al ratios, which provided new opportunities in acid and bifunctional catalysis. This contribution is an overview of the catalytic applications of pore-expanded mesoporous silica and aluminosilica.     

Mo incorporation in MCM-41 type zeolite

Mo-incorporated MCM-41 has been prepared by direct hydrothermal synthesis. XRD and N₂-adsorption measurements showed the characteristics of MCM-41. IR, FT-Raman and UV-VIS DR spectroscopic analyses gave the evidences for the incorporation of Mo in the framework of MCM-41. They are found to be stable and active for cyclohexanol and cyclohexane oxidation reactions with H₂O₂ as oxidant. Activity of this system has been compared with that of Ti-MCM-41 and molybdena impregnated on pure siliceous MCM-41. This revised version was published online in July 2006 with corrections to the Cover Date.     

新型MCM-22/MCM-41复合分子筛上FCC汽油降烯烃芳构化反应

采用纳米组装法合成MCM-22/MCM-41微孔/介孔复合分子筛,分别以H-MCM-22和H-MCM-22/MCM-41为催化剂,在固定床微反装置上对FCC汽油进行降烯烃芳构化的对比考察。结果表明,在反应时间2 h内,与MCM-22相比, MCM-22/MCM-41具有高的芳构化性能和持久的初始活性,复合分子筛汽油改质的产物中,芳烃体积分数由28.58%上升至51.1%,烯烃体积分数由34.04％降至5.8％。探讨了新型H-MCM-22/MCM-41复合分子筛用于FCC汽油改质的操作条件以及催化剂失活再生性能。结果表明,最佳反应条件为：反应温度400 ℃,压力2 MPa,空速3 h^-1。失活催化剂经过两次再生,降烯烃芳构化性能基本不变。