双中孔SiO_2的合成与表征

在通常用于合成中孔ＭＣＭ－４１分子筛的反应体系中,用氨水、ＮａＯＨ或四乙基氢氧化胺作催化剂,在较低的ｐＨ值下合成出具有独特Ｎ２吸附等温线和狭窄双峰中孔分布的双中孔ＳｉＯ２材料。实验表明,在所使用的反应体系中,双中孔ＳｉＯ２结构是一种必然的物相,且反应体系的ｐＨ值调节在合成中起决定性作用。当反应体系的ｐＨ值从约９．５增加到１１时,相应产物的孔径分布由双中孔转变为单中孔分布。这些结果为进一步深入理解中孔材料的形成机理提供了新的视野。合成样品用ＸＲＤ和Ｎ２吸附等温线进行了表征。     

在（TPA）2O—Na2O—SiO2—H2O体系中MFI型硅沸石的结晶行为（Ⅱ）

以白炭黑和硅溶胶为硅源，在（ＴＰＡ）２Ｏ－Ｎａ２Ｏ－ＳｉＯ２－Ｈ２Ｏ体系６０℃下合成了高结晶度纯相硅沸石，由ＳＥＭ没得其晶粒尺寸为０．２μｍ和０．４５μｍ用ＸＲＤ线宽法是的为０．０２μｍ，一１８０℃时合成的硅沸石样品相比，低温合成的细晶粒硅沸石已上备内米级的若干特性，其正己烷吸附量反常增大；ＸＲＤ、ＦＴＩＲ、＾２９ＳｉＭＡＳ ＮＭＲ和ＴＧ／ＤＴＧ／ＤＴＡ的研究证明，其结构破坏温度和单斜／正交对称性     

阴离子X~-(F~-、Cl~-、Br~-)对中孔分子筛MCM-41合成与性质的影响

在凝胶体系ＮａＸ（Ｆ、Ｃｌ、Ｂｒ）Ｎａ２ＯＡｌ２Ｏ３ＳｉＯ２ＣＴＡＢ（十六烷基三甲基溴化铵）Ｈ２Ｏ中，研究了水热合成中孔ＭＣＭ４１的合成条件。实验证明，在３９８Ｋ下晶化８～１６ｄ，ＮａＸ／ＳｉＯ２介于０．０１～０．０５时，均可合成出ＭＣＭ４１分子筛；ＮａＦ的加入，可以加快ＭＣＭ４１分子筛的晶化速度；ＮａＢｒ的加入，对形成ＭＣＭ４１分子筛有阻碍作用。采用ＸＲＤ、ＳＥＭ、ＴＧＤＴＡ和Ｎ２吸附对合成样品加以表征，证明合成样品具有介孔分子筛特性。     

PHASE TRANSFER CATALYZED SYNTHESIS OF DIARYL 2－NITRO－1，4－PHENYLENEDIOXYDIACETATES

ＰＨＡＳＥＴＲＡＮＳＦＥＲＣＡＴＡＬＹＺＥＤＳＹＮＴＨＥＳＩＳＯＦＤＩＡＲＹＬ２－ＮＩＴＲＯ－１，４－ＰＨＥＮＹＬＥＮＥＤＩＯＸＹＤＩＡＣＥＴＡＴＥＳ￥ＸｉＣｕｎＷＡＮＧ；ＴａｉＢａｏＷＥＩ；ＪｉＣｈｏｕＣＨＥＮ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍｉｓ...     

ORIENTATIONAL RELAXATION IN GDEST－HOST AMORPHOUS POLYMERS WITH DEFFERENT GLASS TRANSITION TEMPERATURE

ＯＲＩＥＮＴＡＴＩＯＮＡＬＲＥＬＡＸＡＴＩＯＮＩＮＧＤＥＳＴ－ＨＯＳＴＡＭＯＲＰＨＯＵＳＰＯＬＹＭＥＲＳＷＩＴＨＤＥＦＦＥＲＥＮＴＧＬＡＳＳＴＲＡＮＳＩＴＩＯＮＴＥＭＰＥＲＡＴＵＲＥ￥ＬｉＸｉｎＺＨＥＮＧ；ＴｉａｎＬｕＣＨＥＮ；ＤｅＬｉＷＡＮＧ；Ｘｉ...     

INSITUFTIR SPECTRAL STUDY OF THE OXYGEN ADSPECIES ON SrF_2／La_2O_3 CATALYST DURING THE OXIDATIVE COUPLING OF METHANE

ＩＮＳＩＴＵＦＴＩＲＳＰＥＣＴＲＡＬＳＴＵＤＹＯＦＴＨＥＯＸＹＧＥＮＡＤＳＰＥＣＩＥＳＯＮＳｒＦ＿２／Ｌａ＿２Ｏ＿３ＣＡＴＡＬＹＳＴＤＵＲＩＮＧＴＨＥＯＸＩＤＡＴＩＶＥＣＯＵＰＬＩＮＧＯＦＭＥＴＨＡＮＥ￥ＲｕｉＱｉａｎｇＬＯＮＧ；ＳｈｕｉＱｉｎＺＨＯ...     

PHOTOOXIDATION OF SOME ORGANIC COMPOUNDS CATALYZED BY DECATUNGSTATES

ＰＨＯＴＯＯＸＩＤＡＴＩＯＮ ＯＦ ＳＯＭＥ ＯＲＧＡＮＩＣ ＣＯＭＰＯＵＮＤＳ ＣＡＴＡＬＹＺＥＤ ＢＹ ＤＥＣＡＴＵＮＧＳＴＡＴＥＳ￥ＢｉｎＹＵＥ；ＳｉＳａｎＺＨＵ；ＧａｏＹａｎｇＸＩＥ；ＹｉＤｏｎｇＧＵ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍｉｓｔｒ...     

ASSIGNMENTS FOR THE GROUND STATES OF METAL MONOCARBONYLS

ＡＳＳＩＧＮＭＥＮＴＳＦＯＲＴＨＥＧＲＯＵＮＤＳＴＡＴＥＳＯＦＭＥＴＡＬＭＯＮＯＣＡＲＢＯＮＹＬＳ￥ＸｉｎＸＵ；ＮａｎＱｉｎＷＡＮＧ；ＸｉｎＬＵ；ＱｉａｎＥｒＺＨＡＮＧ（ＳｔａｔｅＫｅｙＬａｂｏｒａｔｏｒｙｆｏｒＰｈｙｓｉｃａｌＣｈｅｍｉｓｔｒｙｏｆ...     

STRUCTURAL STUDIES ON PROTEINS IN MICROEMULSION I．FTIR STUDY ON LYSOZYME IN D_2O／SURFACTANT／n－HEPTANE SYSTEM

ＳＴＲＵＣＴＵＲＡＬＳＴＵＤＩＥＳＯＮＰＲＯＴＥＩＮＳＩＮＭＩＣＲＯＥＭＵＬＳＩＯＮＩ．ＦＴＩＲ　ＳＴＵＤＹＯＮＬＹＳＯＺＹＭＥＩＮＤ_２Ｏ／ＳＵＲＦＡＣＴＡＮＴ／ｎ－ＨＥＰＴＡＮＥ　ＳＹＳＴＥＭＹａｎＬｌ；ＳｈｉＦｕＷＥＮＧ；ＪｉｎＧｕａｎｇＷＵａ?..     

THE STACKING INERACTION OF TERNARY COMPLEXES OF Zn(ATP)~(2-)AND PYRIDINE-LIKELIGANDS

ＴＨＥ　ＳＴＡＣＫＩＮＧ　ＩＮＥＲＡＣＴＩＯＮ　ＯＦ　ＴＥＲＮＡＲＹ　ＣＯＭＰＬＥＸＥＳ　ＯＦ　Ｚｎ（ＡＴＰ）~（２－）ＡＮＤ　ＰＹＲＩＤＩＮＥ－ＬＩＫＥＬＩＧＡＮＤＳＴＨＥＳＴＡＣＫＩＮＧＩＮＴＥＲＡＣＴＩＯＮＯＦＴＥＲＮＡＲＹＣＯＭＰＬＥＸＥＳＯ?..     

用乙二胺和1,6-己二胺作催化剂合成中孔MCM-41分子筛(英文)

首次在温和条件下,用在传统微孔沸石合成中常作为导向剂的乙二胺或1,6-己二胺替代NaOH作催化剂合成出SiO2基中孔MCM-41分子筛。合成样品用XRD和N2吸附等温线进行表征。实验结果表明,由于这种替代,使相应合成样品及焙烧样品的中孔骨架结构的有序度明显提高。在XRD图中四个衍射峰清晰可辨,是典型的六方紧密堆积,晶胞参数a0分别为4.11nm和3.75nm,且d100值随所用胺分子中碳链的增长逐渐从3．56nm减少到3．24nm,同时产物孔径由中孔转变为微孔。     

Formation at low surfactant concentrations and characterization of mesoporous MCM-41

At low concentrations of cetyltrimethylammonium bromide,all silica-based mesoporous materials with hexagonal phase have been synthesized via interactions between self-assembled surfactant molecule aggregates and aniomc silicate polymers.The resulting materials are characterized by XRD,FT-IR,solid state 29Si MAS NMR,thermal analysis and N2 adsorption-desorption measurements.After soluble ions are removed,the interactors between surfactant micelles and silicate polymers are reorganized and then form mesostructures 1 he hexagonal framework is sonsistent with amorphous silica gel.The structures of materials depend on the synthesis conditions Hydrothermal process improves the interactions between molecules and increases the degree of framework silicon atom polymerization The.surface area and the mesopore volume of the material prepared at 100℃ increase by 87% and 71 %,respectively,compared with those obtained at room temperature.     

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.     

多面体倍半硅氧烷制备有序介孔氧化硅材料

Octa(tetramethylammonium)-polyhedral oligomeric silsesquioxane(TMA-POSS) with cage-like structure was synthesized, the structure was characterized by NMR, FTIR and Elemental analyses. The mesoporous silica was prepared under alkaline condition using TMA-POSS as the silicon source and hexadecyltrimethylammonium bromide (CTAB) as the template, the structures of these products were characterized by XRD, TEM and nitrogen adsorption and desorption methods. The results indicate that the synthesized silica exhibites a well-ordered hexagonal pore structure with larger specific surface area. With increasing of CTAB molar ratio, the spacing of the crystal plane d100 is increased. The effects of the pH values on the mesoporous structure in the reaction system with different molar ratio of nPOSS / nCTAB were investigated. The synthesis mechanism of mesoporous silica was also discussed.     

新型高疏水性富含甲基Ti-HMS介孔分子筛的制备、表征和催化性能

通过共缩合和气相甲基接枝两步法制备了新型的高疏水性富含甲基的Ti-HMS介孔分子筛.采用X光衍射、N2吸附、红外光谱、硅核磁、热重、元素分析(原子发射光谱)、紫外可见光谱等手段和亲水性实验对样品进行表征,并用环己烯环氧化反应进行催化性能测试.结果表明,经过两步接枝甲基后,Ti-HMS仍保持典型的介孔结构特征,拥有较多的甲基含量和较高的疏水性,催化环己烯环氧化活性和选择性均比共缩合法(一步接枝法)Ti-HMS有所提高.     

中空介孔二氧化硅锚固聚偕胺肟吸附Cr(Ⅵ)

以硝酸铈铵为引发剂,在自制的中空介孔二氧化硅(HMS)的空腔和通道内引发丙烯腈自由基聚合,并将其氰基偕胺肟化,用于制备具有吸附Cr(Ⅵ)的廉价有机无机复合吸附材料——中空介孔二氧化硅锚固聚偕胺肟.通过傅里叶变换红外光谱(FTIR)、扫描电子显微镜(SEM)及N_2吸附-脱附比表面分析对中空介孔二氧化硅锚固聚偕胺肟进行表征.结果表明,制备的中空微球直径约为400 nm,其壁上孔径约为11.0 nm,比表面积约为431 m~2/g,锚固聚偕胺肟后中空微球壁上孔道直径约为4.6 nm,比表面积降低为347 m~2/g.HMS锚固的聚偕胺肟对重铬酸钾溶液中铬的吸附量高达0.46 mmol/g,吸附过程中伴随化学反应,符合伪二级动力学模型,可用作废水处理中重金属离子的高效廉价吸附材料.     

Synthesis of high surface area Al-containing mesoporous silica from calcined and acid leached kaolinites as the precursors

Al-containing mesoporous silicas were synthesized by hydrothermal treatment of microporous silica prepared by selectively acid leached metakaolinites with Si/Al = 3.9-92.5 mixed with a surfactant of cetyltrimethylammonium bromide (CTABr). The specific surface area of the products increased with higher surfactant/microporous silica (surf/Si) ratio and Si/Al ratio of the microporous silica, reaching about 1400 m2/g at CTABr/Si 0.1 and Si/Al 40. The XRD patterns of these products show a hexagonal (100) peak with the lattice parameter a0=4.2-4.3 nm and the N2 adsorption isotherms show steep increase of adsorption between relative pressure of 0.3 and 0.4. Hexagonal mesoporous microstructure is observed by high resolution TEM. The pore size distributions of the products show a sharp peak at 2.8 nm by the BJH method. The high specific surface area of the present mesoporous samples is attributed to the lower matrix density and surface roughness of mesopore wall. The highest specific surface area of the products reached up to 1420 m2/g and this value is apparently higher than those reported in hexagonal mesoporous silicas. A unique microporous structure of the starting material is thought to be related to achieve such a high specific surface area of the products.     

SBA-15负载CeO2纳米晶的溶胶-凝胶一步合成

以P123为模板剂, 正硅酸乙酯和硝酸铈为前驱体, 通过溶胶-凝胶路线在酸性条件下合成了SBA-15负载氧化铈(CeO2与SiO2质量比为28.7%)有序介孔材料. 采用热重/差热分析(TGA/DTA)、X射线衍射(XRD)、透射电镜(TEM)和氮气吸附等手段对所合成材料进行了表征. 结果表明, 合成的材料具有类似于SBA-15的结构, 孔径、孔容和比表面积分别为38.7 Å, 0.46 cm3/g和570 m2/g. X射线衍射(XRD)、透射电镜(TEM)、X射线能谱(EDS)和选区电子衍射花样联合表征证实了铈物种以高分散的CeO2纳米晶的形式分布在介孔基体中.     

Controlled polymerization in mesoporous silica toward the design of organic-inorganic composite nanoporous materials

Free-radical polymerization inside mesoporous silica has been investigated in order to open a route to functional polymer-silica composite materials with well-defined mesoporosity. Various vinyl monomers, such as styrene, chloromethyl styrene, 2-hydroxyethyl methacrylate, and methacrylic acid, were polymerized after impregnation into mesoporous silicas with various structures, which were synthesized using polyalkylene oxide-type block copolymers. The location of the polymers was systematically controlled with detailed structures of the silica framework and the polymerization conditions. Particularly noteworthy is the polymer-silica composite structure obtained by in situ polymerization after the selective adsorption of monomers as a uniform film on silica walls. The analysis of XRD data and the N(2) adsorption isotherms indicates the formation of uniform polymer nanocoating. The resultant polymer-silica composite materials can easily be post-functionalized to incorporate diverse functional groups in high density, due to the open porous structure allowing facile access for the chemical reagent. The fundamental characteristics of the composite materials are substantiated by testing the biomolecule's adsorption capacity and catalytic reactivity. Depending on the structure and composition of polymers, the resultant polymer-silica composite materials exhibit notably distinct adsorption properties toward biomolecules, such as proteins. Furthermore, it is demonstrated that the nanocoatings of polymers deposited on the mesopore walls have remarkably enhanced catalytic activity and selectivity, as compared to that of bulk polymer resins. We believe that, due to facile functionalization and attractive textural properties, the mesoporous polymer-silica composite materials are very useful for applications, such as adsorption, separation, host-guest complexes, and catalysis.