水玻璃为原料在开放体系中快速合成介孔材料MCM-41

自从 M41 S系列硅基介孔分子筛被人工合成以来[1,2 ] ,有关分子筛的合成、性能、形成机理、结构和应用等方面的研究报道不断出现[3～ 5] .目前 ,由有机 -无机离子经分子水平的自组装结合而产生介孔材料的合成机理主要归结于在合成过程中表面活性剂的模板效应 ,如液晶模板机理[1,2 ] 、棒状自组装模型[6 ] 、电荷匹配机理[7] 、层状折皱模型[8] 和使用非离子表面活性剂合成介孔材料等效应[9] .本文以水玻璃作为硅源 ,以十六烷基三甲基溴化铵 (CTAB)阳离子表面活性剂为模板剂 ,在温和条件下 ,采用开放体系合成出具有 MCM-4 1结构特点的介…     

苯及苯磺酸基官能化的中孔分子筛的合成及催化应用

近年来 ,通过对介孔分子筛 (如 MCM,HMS,MSU-X)结构及组成的化学“裁剪”,制备具有特定结构和表面性质的催化材料成为该领域的研究热点之一 [1～ 5] .许多文献报道了 MCM-4 1的有机官能化中孔材料的制备技术 [5～ 8] ,并将其应用于有机合成反应 ,取得了较好的结果 [7,8] .其中 MSU-X介孔分子筛结构具有三维排列“Worm-like”孔道特征 ,有利于物料传输 ;相对于 MCM-4 1分子筛在合成方面具有以中性表面活性剂作模板剂且模板剂容易去除等诸多优点[9] .本文采用非离子表面活性剂 C11— 15H2 3— 31(CH2 CH2 O) 9H(AEO9)为模板剂 ,…     

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。     

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。     

钛硅沸石分子筛TiMCM-41的微波合成与表征

ＭＣＭ４１分子筛是一类以表面活性剂季铵碱或季铵盐为模板剂,液晶模板机理合成,孔道六方有序排列,孔径大小可在１６～１０ｎｍ范围内调节的新颖中孔硅铝分子筛材料．在多相催化、离子交换、吸附分离以及高等无机材料等领域具有较高的工程应用与学术研究价值［１］...     

内嵌型介孔分子筛的合成

用表面活性剂十六烷基三甲基氢氧化铵在溶液中形成的液晶相胶态分子团作为模板剂，同时在分子团憎水基团内部导入对乏燃料中钯离子有特效选择萃取效应的协萃剂ＴＯＰＯ－Ｐ２０４，通过表面活性剂亲水基团与易水解的有机硅酸盐阴离子之间的自组织过程，合成了内嵌型介孔分子筛固体吸附剂ＭＣＭ－ＴＰ，经ＴＥＭ，ＸＲＤ，２９Ｓｉ－ＭＡＳＮＭＲ测试，与ＭＣＭ－４１介孔分子筛有相似的孔道结构，但其晶胞参数有所增加，水热稳定性有明显的改善．用于提取乏燃料中的钯，饱和吸附Ｐｄ容量可达０．０１５ｍｍｏｌ／ｇ．     

介孔分子筛的酸性和水热稳定性

介孔分子筛材料在催化、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潜在的应用价值.但是,由于介孔分子筛材料较低的水热稳定性和较弱的酸性,极大地影响了其在催化研究中的广泛应用.本文系统地综述了最近几年在提高介孔分子筛酸性和水热稳定性的研究工作.其中包括:(1)将超酸组份负载于介孔分子筛的孔道中以达到提高介孔分子筛材料的酸强度的目的;(2)通过在合成介孔分子筛的过程中加入无机盐和有机胺等助剂或采用合适的后处理方法以提高介孔分子筛的水热稳定性;(3)通过新型模板剂来合成具有较高水热稳定性的介孔分子筛材料;(4)利用具有沸石分子筛基本结构单元的沸石分子筛导向剂与表面活性剂自组装来合成具有强酸中心和高温水热稳定的介孔分子筛材料.     

具有强酸位的六方和立方介孔硅铝分子筛合成及催化活性比较

六方 MCM- 41和立方 MCM- 48介孔分子筛是长程有序的介孔材料 ,由于其孔壁是无定形结构 ,具有较弱的酸性 ,限制了其应用范围 .若能提高它们的酸强度则可提高其在石油炼制和精细化工中的应用价值 .现已采用多种改进方法来提高其酸强度 [1～ 6 ] ,但所合成的介孔材料均为六方结构 ,而具有立方结构的材料未见文献报道 .本文采用两步晶化合成法 ,用低浓度的表面活性剂合成出具有强酸位的立方介孔分子筛 ( MB48) ,还通过调节溶液的酸碱性合成出六方介孔分子筛 ( MB41 ) ,对样品的结构、酸性和催化性能进行了表征和比较 .1　实验部分1 .1　 β…     

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.     

有机小分子模板法合成二氧化钛中孔材料

1992年美国Mobil公司[1,2]首次以表面活性剂为模板,合成出具有特定孔道结构和规则孔径的中孔分子筛.近7年来以离子或中性表面活性剂为模板制备硅中孔或过渡金属掺杂的中孔材料的报道层出不穷[3,4].由于这些材料的孔径较大,分布均匀,以及过渡金属的特殊催化性能使其在分离或催化中得到应用.1998年Wei[5]等首次以葡萄糖、麦芽糖和酒石酸衍生物等非表面活性剂有机分子为模板,制备出高比表面积,孔径可调,窄孔径分布的中孔二氧化硅分子筛.由于有机小分子种类繁多,后处理方便,且有的对环境友好,这为中孔材料的制备提供了一种新方法.迄今为止,以过…     

混合超分子液晶模板法合成六方介孔相含钛氧化硅

采用混合十六烷基三甲基溴化铵（CTAB）与不同碳链的脂肪胺（CnNH2n＋3, n=8,10,12,14,16）作模板,在四甲基氢氧化胺为碱源的条件下,合成了具有六方介孔结构的含钛氧化硅Ti MCM 41分子筛材料. XRD和TEM测试表明所合成材料具有高度的长程有序结构,样品的N2吸附/脱附等温线表明,高度有序的Ti MCM 41材料展示了毛细凝聚的陡峭台阶和狭窄的介孔孔径分布.对反应物配比中Ti/Si比、脂肪胺碳链长度n对六方介孔相结构的影响进行了研究,实验发现当Ti/Si< 0.15和n< 16时,均可获得具有六方介孔结构的含钛氧化硅Ti MCM 41;而当Ti/Si≥0.15或n >16时,产物将分别发生从六方向无定形态或从六方向层状介孔相结构的转移,从混合表面活性剂的堆积参数对这种相转移现象进行了分析.     

Synthesis of Cubic Mesoporous Silica MCM-48by Mixed Micellar Templates

In 1992, Mobil researchers introduced a novel concept in the synthesis of mesoporous silicas (M41S)1,2 by using a self-assembled molecular array of surfactant molecules as structure-directing template. Depending on the shape of their templates and the respective resulting pore structure, the M41S family was identified : MCM-41(hexagonal), MCM-48(cubic), and other species. MCM-41 with honeycomb arrays of nonintersecting channels was shown to be the easiest to synthesize1. MCM-48 containin…     

纯二氧化钛介孔分子筛的合成与表征

分别用不同链长的烷基磷酸酯和脂肪胺两类不同表面活性剂为模板剂合成了纯二氧化钛介孔分子筛（Ti-TMS1，Ti-TMS2），并用溶剂法代替高温焙烧法成功地脱除了模板剂。用 XRD、TEM等测试手段对这类材料的结构进行了表征，研究了反应条件对所制备样品的结构的影响。结果表明：得到的纯二氧化钛介孔分子筛为较规则的六角堆积排列，孔径为2.7～4.4 nm, 且其纳米孔径大小可以通过改变烷基磷酸酯模板剂的烷基链长而调节。此外还发现，采用的烷基磷酸酯模板剂的烷基链越长，制得的二氧化钛介孔分子筛结构及晶型的完整性越好。进一步的研究表明，模板剂脱除之后，Ti-TMS2结构的晶体完整性和稳定性明显不如Ti-TMS1的好，且Ti-TMS1的介孔结构优于Ti-TMS2的介孔结构。     

正、负离子表面活性剂混合体系溶致液晶生成的相行为

研究了烷基(C8,C12,C14)三甲基溴化铵、烷基(C12,C14)溴化吡啶与烷基(C8,C12)硫酸钠混合体系溶致液晶形成的条件与结构的变化.在高浓度的水溶液中,随着正、负离子表面活性剂摩尔比接近于1,液晶结构由六角相过渡为层状相.表面活性剂非极性链长改变,对相行为影响显著,短碳链的正、负离子表面活性剂混合体系,在等摩尔比时,体系为层状液晶或立方液晶为主,夹杂少许沉淀.随碳链增长,两类表面活性剂间的静电吸引效果表现为生成沉淀的摩尔比例范围变宽,沉淀量增多,共存的液晶相减少,甚至消失.若只改变正离子的极性头基,季胺盐比吡啶盐与烷基硫酸盐的作用要强,形成不溶物的混合摩尔比例范围更宽.     

Versatile phase transfer of gold nanoparticles from aqueous media to different organic media

A novel, simple, and very efficient method to prepare hydrophobically modified gold particles is presented. Gold nanoparticles of different sizes and polydispersities were prepared. The diameter of the gold particles ranges from 5 to 37 nm. All systems were prepared in aqueous solution stabilized by citrate and afterwards transferred into an organic phase by using amphiphilic alkylamine ligands with different alkyl chain lengths. The chain length was varied between 8 and 18 alkyl groups. Depending on the particle size and the alkylamine, different transfer efficiencies were obtained. In some cases, the phase transfer has a yield of about 100%. After drying, the particles can be redispersed in different organic solvents. Characterization of the particles before and after transfer was performed by using UV/Vis spectroscopy, transmission electron microscopy (TEM), and small-angle X-ray scattering (SAXS) techniques. The effect of organic solvents with various refractive indices on the plasmon band position was investigated.     

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.     

X-ray diffraction study of the structure of carboxymethylcellulose-cationic surfactant complexes.

We have investigated dilute aqueous solutions of an anionic polymer (carboxymethylcellulose) mixed with cationic surfactants of different chain lengths (dodecyl to octadecyl trimethylammonium bromides: DTAB, TTAB, CTAB and OTAB). The structures of the concentrated phases formed above the precipitation threshold were studied by X-ray diffraction. Different body-centred cubic structures with space groups Pm3n were observed in the presence of surfactant with a short aliphatic chain (DTAB), despite the fact that the polymer persistence length is comparable to the repeat distance of the structure (5 nm). For larger surfactant chain lengths (TTAB and CTAB), the structure of the precipitates can be either cubic (Pm3n) or 2D hexagonal depending on the initial surfactant and polymer concentrations. For still larger chain length (OTAB), the structure becomes lamellar. This structural evolution from micellar cubic towards 2D hexagonal and lamellar is attributed to the decrease of the local curvature of the surfactant aggregates, as observed for flexible synthetic polymers and short DNA fragments under similar conditions. Furthermore, the structure of the bulk complexes formed just below the precipitation threshold anticipates the structure seen in the precipitated phases.     

Mixed micelles of alkylamines and cetyltrimethylammonium chloride

The influence of chain length and the nature of the head group on the composition of micelles of a binary mixture of cetyltrimethylammonium chloride with both unsubstituted and N-substituted n-octyl, n-decyl, and n-lauryl amines was established from the variation of the critical micelle concentration (cmc) as a function of the solution composition. A synergistic effect was observed in all instances that were found to be correlated with chain length and the type of N-substituent on the alkylamine head group. Experimental data were compared with theoretical predictions based on the equilibrium between micelles and monomers in solution. The Motomura treatment was used to determine the composition of each compound in the mixed micelles (Xi(m)). Mixing nonideality was expressed in terms of the molecular interaction parameter (beta12) as determined using the theory of Holland and Rubingh. Finally, the molecular thermodynamic model for mixed surfactant systems developed by Puvvada and Blankschtein was used to estimate the micellization free energy (DeltaGM) and to evaluate the synergistic phenomenon.     

Size control and growth process of alkylamine-stabilized platinum nanocrystals: a comparison between the phase transfer and reverse micelles methods

Alkylamine-stabilized platinum nanoparticles are synthesized either by the phase-transfer method or in reverse micelles. The phase-transfer method produces nanocrystals that are quite spherical whereas the synthesis in reverse micelles generates a large number of wormlike structures. An alkylamine is used as a stabilizing agent to prevent nanoparticle coalescence, and it is shown that there is an inverse relationship between the alkylamine chain length and the platinum nanoparticle diameter. By comparing alkylamine and alkylthiol analogues, it is found that the integrity of the different crystallites depends on the strength of the interaction between the stabilizing agent and the platinum nanocrystals. The results obtained and the comparison made between the two synthesis methods improve the understanding of the growth mechanisms of platinum nanocrystals in disperse media.