β沸石的铝化

β沸石自1988年结构被确定以来受到普遍重视,由干结构上的特殊性,G沸石既具有较强酸性又具有明显的碱性［‘,‘］．但q佛石的高硅铝比使其在化学组成上对碱性的贡献甚微,如果能降低其硅铝比,则有可能获得具有较强碱性的佛石分子筛．直接合成的o佛石,硅铝比一般在10以上．     

XeF和KrF的热催化合成及KrF在含氟高能氧化剂NFBF合成中的应用

本文介绍了一种以氟气和惰性气体为原料合成 Kr F2 和 Xe F2 的热催化合成方法并对合成机理和条件作了简单的讨论 ,利用合成的 Kr F2 作为氟化剂合成了含氟高能氧化剂 NF4BF4,纯度约为 93%,其红外光谱和拉曼光谱基本与文献值吻合。元素分析结果表明产品 NF4BF4中含 B5.8%(mass) ,自由氟原子含量为 9.95%(mass) ,与理论值基本一致 ,此结果也间接证明了 Kr F2 质量的可靠性。粉末状的 Xe F2 经升华 -再结晶纯化后可得纯净晶体产品。     

TCDD的密度泛函理论研究

用B3LYP/6-311G~(**)方法全优经计算22个四氯二苯并对二（左口右恶）英（ 简称TCDD）分子，得到几何构型、总能量、标准熵、标准焓和标准自由能。将2， 3，7，8－TCDD的计算构型与X射线衍射实验测定值进行了比较。计算结果表明，总 能量、标准焓和标准自由能与氯原子量换位置的相关性很高（r > 0.997）.1,3,6, 8-TCDD的总能量处自由能最低，即最稳定，以此参照，得到异构体的总能量的相对 稳定性顺序和自由能的相对稳定性顺序。1,3,7,9－TCDD的稳定性次之，1,3,7,8- TCDD居第三，将这二个顺序与焚烧炉产生的TCDD异构体和合成的异构体对的生成面 分比进行了比较，说明焚烧炉中产生的TCDD和合成的TCDD对的分布主要受热力学控 制。     

Synthesis, X-ray crystal structures, and gas sorption properties of pillared square grid nets based on paddle-wheel motifs: implications for hydrogen storage in porous materials

A systematic modulation of organic ligands connecting dinuclear paddle-wheel motifs leads to a series of isomorphous metal-organic porous materials that have a three-dimensional connectivity and interconnected pores. Aromatic dicarboxylates such as 1,4-benzenedicarboxylate (1,4-bdc), tetramethylterephthalate (tmbdc), 1,4-naphthalenedicarboxylate (1,4-ndc), tetrafluoroterephthalate (tfbdc), or 2,6-naphthalenedicarboxylate (2,6-ndc) are linear linkers that form two-dimensional layers, and diamine ligands, 4-diazabicyclo[2.2.2]octane (dabco) or 4,4'-dipyridyl (bpy), coordinate at both sides of Zn(2) paddle-wheel units to bridge the layers vertically. The resulting open frameworks [Zn(2)(1,4-bdc)(2)(dabco)] (1), [Zn(2)(1,4-bdc)(tmbdc)(dabco)] (2), [Zn(2)(tmbdc)(2)(dabco)] (3), [Zn(2)(1,4-ndc)(2)(dabco)] (4), [Zn(2)(tfbdc)(2)(dabco)] (5), and [Zn(2)(tmbdc)(2)(bpy)] (8) possess varying size of pores and free apertures originating from the side groups of the 1,4-bdc derivatives. [Zn(2)(1,4-bdc)(2)(bpy)] (6) and [Zn(2)(2,6-ndc)(2)(bpy)] (7) have two- and threefold interpenetrating structures, respectively. The non-interpenetrating frameworks (1-5 and 8) possess surface areas in the range of 1450-2090 m(2)g(-1) and hydrogen sorption capacities of 1.7-2.1 wt % at 78 K and 1 atm. A detailed analysis of the sorption data in conjunction with structural similarities and differences concludes that porous materials with straight channels and large openings do not perform better than those with wavy channels and small openings in terms of hydrogen storage through physisorption.     

A Facile Synthesis of Ethyl 2,4-Dimethoxy-6-perfluoroalkyl-benzoates via Acyclic Precursors

Introduction Polysubstituted arenes are important intermediates in synthetic medicines and dyestuffs, and the fluorinated analogues are more attractive as a result of their lipo-philicity and the increment of activity.1,2 Therefore, to study the convenient and efficient synthesis of polysub-stituted arenes is valuable in organic synthetic method-ology. We have designed a simple synthesis of fluori-nated polysubstituted arenes through the intramolecular Wittig reaction of a new phosphorous ylid…     

溶胶-凝胶法制备铁酸盐超微粒子催化剂

采用溶胶－凝胶法制备了含Zn,Ni,Co的铁酸盐超微粒子催化剂，运用DTA－TG、IR、XRD以及BET比表面测试等手段对所制备的样品进行了表征。同时，考察了铁酸盐对二氧化碳选择性氧化乙苯制苯乙烯的催化性能。结果表明：制备的铁酸盐均为尖晶石型晶体，粒子的比表面积为31．9－36．3m^2/g，晶粒大小约为30－35nm，在由二氧化碳选择性氧化乙苯制苯乙烯的反应中表现出较好的催化活性。     

Facile synthesis of 9-（N-amino-4-fluoromethyl-3-pyrrolidinyl）-2- fluoro-6-aminopurine from trans-4-hydroxy-L-proline

A novel and simple procedure for synthesis of azanucleoside by Mitsunobu reaction between N-(p-nitrobenzyloxycarbonyl)- trans-4-hydroxy-D-proline methyl ester obtained from trans-4-hydroxy-L-proline after six-step reaction and 2-fluoro-6-azidopurine is described,and azanucleoside is fluorinated by new fluridizer 2,2-difluoro-1,3-dimethylimidazolidine (DFI).All reactions could be carded out under mild condition.     

A Novel Cu-Mo／ZSM-5 Catalyst for NOx Catalytic Reduction with Ammonia

The Cu-Mo/ZSM-5 catalysts with different Cu/Mo ratios were prepared by wet impregnation method, and their catalytic performance for selective catalytic reduction of NOx was studied. The results showed that Cu-Mo/ZSM-5 is a very effective catalyst for NOx catalytic reduction with ammonia, especially when Cu/Mo molar ratio is about 1.5. It not only exhibited the extremely high catalytic activity, but also showed good stability for 02. The bulk phase structure of Cu-Mo/ZSM-5 catalysts was determined by XRD technique, and the results indicated that there is a maximum dispersion for Cu species when Cu/Mo molar ratio is 1.5, and an interaction between Cu and Mo along with HZSM-5 may be present in Cu-Mo/ZSM-5, which may possibly result in a special structure favorable for the catalytic reduction of NOx over Cu-Mo/ZSM-5 catalyst.     

微铂电极上1-酰基二茂铁动力学参数的测定

本文合成并研究了１－酰基二茂铁在ＣＨ２Ｃｌ２中的伏安行为，测定了它们在ＣＨ２Ｃｌ２中不同支持电解质浓度时的扩散系数，并分明用Ｚ．Ｇａｌｕｓ和Ｋ．Ａｏｋｉ方法计算了两种状态下的电子迁移速率常数。讨论了取代基的诱导效应和共轭效应及其链长对１－酰基二茂铁的动力学性质的影响以及支持电解质及其浓度等因素对伏安曲线的影响。