Combinatorial Approach to the Hydrothermal Synthesis of Zeolites

One hundred or more solid-state syntheses can be conducted in parallel and employed for the combinatorial hydrothermal syntheses of zeolites by using a novel multiautoclave design. The operation of the multiautoclave was ascertained by the reinvestigation of the complete Na₂O-Al₂O₃-SiO₂ ternary system in a single experiment. In the picture on the right, the shaded areas on the left show the crystallization fields of the different phases obtained.     

有机硅骨架修饰的磷酸铝分子筛VPI-5的合成

分别以1,2-双(三乙氧基硅基)乙烷(BTESE)、1,2-双(三乙氧基硅基)乙烯(BTESEE)和苯基三乙氧基硅烷(PTES)为硅源, 通过一步法直接合成有机硅骨架修饰的磷酸铝分子筛VPI-5. 系统考察了各反应参数对产物结构与性质的影响, 并对产物的结构进行了表征. 表征结果表明, 有机基团通过硅原子被引入到分子筛骨架中. 有机基团的引入增加了分子筛的亲油性, 并且不同的有机基团对分子筛的亲油性的提高程度不同.     

Synthesis and Characterization of Magnesium Substituted Aluminophosphate Molecular Sieves with AEL Structure

MAPO-11 molecular sieves were synthesized by hydrothermal methods. The influence of precursor of magnesium, Mg/Al ratio, synthesis temperature, synthesis time and the type of template on the formation and properties of MAPO-11 molecular sieves was examined. The samples were characterized by the techniques of X-ray diffraction (XRD), scanning electron microscopy (SEM), thermogravimetric/differential thermogravimetric analysis (TG-DGA), etc. The results show that the shape and size of crystal were influenced by the precursor of Mg, the Mg/Al ratio and the type of template, and the TG-DGA analysis shows that MAPO-11 molecular sieves as-synthesized have poor thermal stability.     

利用新型模板剂合成中孔分子筛催化剂的研究

利用新型模板剂合成中孔分子筛催化剂的研究张小明张兆荣索继栓１）李树本（中国科学院兰州化学物理研究所精细石油化工中间体国家工程研究中心兰州７３００００）关键词新型模板剂中孔分子筛水热合成分类号Ｏ６４３．３２９０年代以来，中孔分子筛的合成与应用研究已经成...     

Synthesis of Aluminophosphate Molecular Sieves in Alkaline Media

Unlike conventional aluminosilicate zeolites synthesized in alkaline media, aluminophosphate molecular sieves (AlPOs) have always been prepared under acidic conditions in the past three decades; this has been regarded as one of essential factors for synthesis, except for the case of silica-substituted analogues (SAPOs). For the first time, we demonstrate herein a simple and generalized route for synthesizing various types of aluminophosphate molecular sieves in alkaline media. A series of aluminophosphate sieves and their analogues have been prepared with different quaternary ammonium cations as structure-directing agents in this manner. The above successes have extended the systematic media from acidic or neutral to alkaline for the preparation of a series of aluminophosphate molecular sieves, which possibly open an alternative route for the synthesis of aluminophosphate molecular sieves.     

钛酸盐分子筛的合成研究

以ＴＰＡＯＨ和ＴＥＡＯＨ模板剂分别合成了具有孔道结构的钛酸铜、钛铝酸钠和钛酸钠分子筛，采用Ｘ射线衍射，红外光谱，紫外光谱，扫描电镜，差热分析、ＮＨ３－脱附法及气体吸附法等测试手段对钛酸盐分子筛的物性及结构进行了表征。利用苯酚羟基化反应及气相色谱法证明了具有四配位ＴｉＯ４结构单元的钛酸铜分子筛的催化氧化性能。     

新型磷酸铝分子筛AlPO_4-CJ_2的合成与结构研究

在Al_2O_3-P_2O_5-六次甲基四胺-H_2O体系中,水热合成出新型磷酸铝分子筛(AlPO_4-CJ_2),培养了单晶,经多晶X射线衍射、四圆单晶结构测定及红外光谱研究证明,AlPO_4-CJ_2具有空旷的骨架结构,沿(100)和(001)方向具有8元环孔道,骨架中Al原子以AlO_5(三角双锥)和AlO_5F(扭曲八面体)形式存在,水分子氧的桥联产生Al—O—Al连接模式。     

Strategies for the Dynamic Integration of Combinatorial Synthesis and Screening

Selection and amplification of only those components with the desired property–the integration of combinatorial chemistry and screening makes this possible. If the components of a combinatorial library are in a reversible equilibrium, the desired components can be selected and amplified by shifting the equilibrium of the mixture (see schematic representation).     

Combinatorial Synthesis of Small Organic Molecules

Combinatorial synthesis has developed within a few years from a laboratory curiosity to a method that is taken seriously in drug research. Rapid progress in molecular biology and the resulting ability to determine the activity of new substances extremely efficiently have led to a change in paradigm for the synthesis of test compounds: in addition to the conventional procedure of synthesizing one substance after another, new methods allowing simultaneous creation of many structurally defined substances are becoming increasingly important. A characteristic of combinatorial synthesis is that a reaction is performed with many synthetic building blocks at once—in parallel or in a mixture— rather than with just one building block. All possible combinations are formed in each step, so that a large number of products, a so-called library, is obtained from only a few reactants. Several methods have been developed for combinatorial synthesis of small organic molecules, based on research into peptide library synthesis: single substances are produced by highly automated parallel syntheses, and special techniques enable targeted synthesis of mixtures with defined components. Many structures can be obtained by combinatorial synthesis, and the size of the libraries created ranges from a few individual compounds to many thousand substances in mixtures. This article gives an overview of the combinatorial syntheses of small organic molecules reported to date, performed both in solution and on a solid support. In addition, different techniques for identification of active compounds in mixtures are presented, together with ways to automate syntheses and process the large amounts of data produced. An overview of pionering companies active in this area is also given. The final outlook attempts to predict the future development of this exponentially growing area and the influence of this new thinking in other areas of chemistry.     

硼酸盐分子筛的合成及其结构研究

在Na_2O-CaO(MgO)-Al_2O_3-B_2O_3-R-H_2O体系中用水热法合成了2种新型的微孔硼铝酸盐。XRD、IR和XPS分析表明,它们具有新的骨架结构。在一定温度下脱除结构中的游离水及其它分子后,所得产物表现出特征的分子筛吸附性能。吸附性能的测定结果及孔径分布的计算表明,其孔径大小在5～6之间。     

Gel Chemistry in Synthesis of AIPO4 Molecular Sieves

The chemistry of ternary systems, Al₂O³-P₂O₅-H₂O, particularly on addition of an acid or an amine as fourth component was investigated with ³¹P and ²⁷Al NMR spectroscopy.     

Combinatorial Material Libraries on the Microgram Scale with an Example of Hydrothermal Synthesis

In a 8-μL multichambered microreactor (the photo shows the components) material libraries can be produced in a simple manner through combinatorial hydrothermal synthesis. In a model experiment the synthesis of the zeolite TS-1 has been varied combinatorially. The resulting library is characterized directly by automated microdiffraction.     

Synthesis of Microporous Transition Metal Oxide Molecular Sieves with Bifunctional Templating Molecules

Systematic tuning of the micropore size in microporous transition metal oxide molecular sieves can be achieved by varying the length of the hydrocarbon chain of the diamine molecules used as templating agents. The large bifunctional molecules self-assemble with much smaller cross-sectional micellar dimensions than their monofunctional counterparts. The resulting family of porous materials offers exciting new flexibility in designing molecular sieves targeted for size selectivity and chemical functionality.     

Combinatorial Solid-Phase Synthesis of Structurally Complex Thiazolylhydantoines

A nine-step (!) solid-phase synthesis and subsequent cleavage with cyclization from the polymeric support were the keys to preparing high-quality molecular libraries of thiazolylhydantoines 1 from modified amino acid building blocks. Each step in the synthesis is different. Because the final cyclization cleaves only molecules that have been successfully constructed, the products obtained are pure. R¹, R²=alkyl; R³=aryl, arylO; R⁴=allyl.     

MeAPO-5分子筛的合成及其在肉桂醇选择氧化反应中的催化性能

采用水热法合成了一系列杂原子磷铝分子筛MeAPO-5(Me=Co,Fe,Cu,Zn,Mn),并利用X射线衍射(XRD),热重-差热分析(TG-DTA),电感耦合等离子体原子发射光谱(ICP-AES)和漫反射紫外-可见光谱(DRUV-Vis)等技术对分子筛的结构,化学组成以及金属离子的存在状态进行了表征.结果表明,合成的纯相MeAPO-5分子筛具有较高的结晶度,金属杂原子种类显著影响其在MeAPO-5分子筛中的存在状态,取代度及合成样品的结晶度.Co2+,Fe3+,Zn2+和Mn2+较易进入分子筛骨架,而Cu2+较难进入.通过考察MeAPO-5分子筛在肉桂醇氧化反应中的催化性能,发现CoAPO-5分子筛具有良好的选择氧化催化性能,1,4-二氧六环是较好的溶剂,调变反应温度可以有效调控产物的选择性.     

沸石类分子筛合成研究新进展

对当前国际上沸石和沸石类分子筛材料的合成研究进行了综述, 分析了合成研究动向, 指出了合成研究中值得注意的几点问题, 并提出了研究展望。     

Synthesis and Characterization of the Large Pore Molecular Sieves VPI-5 and Si-VPI-5

The large pore molecular sieves VPI-5 and Si VPI-5 were synthesized by using three organic amines (dipropylamine, diisopropylamine and dipentylamine) as the structure-directing agents. Compared with general alumlnophosphate molecular sieves, the synthesis of the molecular sieves of VPI-5 type ls of many unique features. Both VPI-5 and Si-VPI-5 were characterized by XRD, IR, TG-DTA, and MAS-NMR.     

Preparation and Spectral Analysis of Nickel-containing Aluminophosphate Molecular Sieves of Type-5

Diffuse reflectance spectroscopy was used to studynickel ion positions in the aluminophosphate molecularsieves of the AlPO-5 type. Nickel ions wereintroduced into the reactant mixture of thealuminophosphate and the synthesis carried outhydrothermally through various methods of gel, clearsolution and diluted suspension. The visibleabsorption spectra obtained of the dried, hydrated andcalcined materials were studied. A distinct andwell-defined triplet absorption band observed at about625, 580 and 540 nm was assigned to tetrahedralframework-substituted nickel(II) ions. A relativelystrong band at about 400 nm and two broad bands withsimilar intensity at 730 and 660 nm were assigned tooctahedral nickel species. These 730 and 660 nm bandsare observable only in the sample where nickel cationswere incorporated merely in the octahedralextra-framework sites by ion-exchange treatment ofSAPO-5. According to the synthesis procedure used,the amount of tetrahedral framework-substituted nickelions in comparison with octahedral ones can beevaluated from the intensities of the characteristicbands of the 4- and 6-coordinated nickel ions. Thereis much more octahedral nickel compared with thetetrahedral ones estimated in the light of theintensity data taking into account the absorptivitiesof nickel (II) symmetries. This work showed thatusing our synthesis procedure of a dilutedsuspension will result in preparing NiAPO-5 molecular sieve with more nickel cationsincorporated in the framework sites ofthe aluminophosphate. A very small quantity of thesecations remain in their sites at temperatures as highas 550°C.     

固相合成及组合化学用的高聚物载体

综述了用于固相合成及组合化学的高聚物载体的制备方法、特征、应用和最新进展,重点介绍了目前广泛用作固相载体的交联聚苯乙烯树脂、聚酰胺树脂和TentaGel树脂,并对几类新型载体如聚乙二醇、聚四氢呋喃衍生物交联剂改性的聚苯乙烯树脂、非芳环体系的POEPOP,树脂和SPOCC树脂作了简要的概述。