过渡金属硼酸盐K7{(BO3)Zn[B12O18(OH)6]}·H2O的合成与量子化学研究

通过水热的方法合成了一例新的过渡金属硼酸盐K7{(BO3)Zn[B12O18(OH)6]}·H2O(1),并对其进行了红外,热重,能谱以及X-射线单晶衍射和粉末衍射分析。晶体学测试结果表明,化合物1属于正交晶系,Pmn21空间群,晶胞参数a=1.236 51(4)nm,b=0.909 61(3)nm,c=1.304 05(5)nm,V=1.466 72(9)nm3,Z=2,R1=0.049 7,wR2=0.146 8。对{(BO3)Zn[B12O18(OH)6]}7-阴离子簇的量化分析显示此簇中的端基BO3基团对前线分子轨道的贡献最大。除端O原子外,BO3端基的原子电荷较其它B和O原子电荷低。     

固体粒子对板式膜吸收过程的传质强化

分别采用纯CO2-去离子水和不同浓度的NaOH溶液为实验体系,在板式膜器中研究了第三相固体粒子对膜吸收过程传质效果的影响．分别考察了在不同粒子种类、搅拌转速、传质体系、化学反应强度、膜孔隙率等因素下固体粒子对传质强化的影响．结果表明,随着粒子固含率的增大,传质系数和增强因子均有所提高,当粒子固含率增大到一定范围后,传质系数和增强因子的变化趋于平缓．在固含率一定的条件下,不同种类的固体粒子对膜吸收过程的强化效果随着固体粒子密度的增加而减小．传质系数随着搅拌转速的增大而增大,但高搅拌转速下固体粒子的强化作用减弱．膜吸收过程的传质系数和增强因子随着化学反应强度的增强而增加．随着粒子固含率的增大,不同膜孔隙率对传质效果的差异减小,且孔隙率越小,固体粒子对膜吸收传质过程的强化效果越好．其中,对于纯CO2-去离子水体系,当孔隙率为20％,粒子固含率为1．5gL^（-1）时,固体粒子的加入可使传质系数提高1．45倍,增强因子可达2．45．     

Rh-TPPTS/CTAB-MMT催化剂的制备及其催化长链烯烃氢甲酰化反应性能研究

通过浸渍法将水溶性铑膦配合物(Rh-TPPTS)负载到由十六烷基三甲基溴化铵(CTAB)修饰的蒙脱土(MMT)上,制备出Rh-TPPTS/CTAB-MMT负载型催化剂.采用XRD,FTIR,TG,BET,31P CP-MAS NMR和分散性实验对催化剂进行了表征.结果表明:水溶性铑膦配合物成功地负载到有机MMT上,并且该催化剂在有机溶剂中具有很好的分散性.该催化剂对于1-癸烯的氢甲酰化反应具有好的催化活性.在100℃、4 MPa、甲苯为溶剂的条件下,催化1-癸烯氢甲酰化可获得93.0%的转化率,95.8%的醛的选择性,2.1的正异比,137 h-1的TOF值.并对不同链长烯烃底物进行了考察.随着烯烃碳链的增加,醛的选择性下降,但是正异比有所增加.     

SYNTHESIS OF A SILICA－SUPPORTED CARBOXYMETHYL CELLULOSE PLATINUM COMPLEX AND ITS CATALYTIC BEHAVIORS FOR HYDROGENATION OF ETHYL BENZOATE

ＳＹＮＴＨＥＳＩＳ ＯＦ ＡＳＩＬＩＣＡ－ＳＵＰＰＯＲＴＥＤ ＣＡＲＢＯＸＹＭＥＴＨＹＬ ＣＥＬＬＵＬＯＳＥ ＰＬＡＴＩＮＵＭ ＣＯＭＰＬＥＸ ＡＮＤ ＩＴＳ ＣＡＴＡＬＹＴＩＣ ＢＥＨＡＶＩＯＲＳ ＦＯＲ ＨＹＤＲＯＧＥＮＡＴＩＯＮ ＯＦ ＥＴＨＹ...     

Alkylation of Benzene with Propene over Hβ Zeolite──The Effect of Reaction Conditions on the Distribution of Products

ＡｌｋｙｌａｔｉｏｎｏｆＢｅｎｚｅｎｅｗｉｔｈＰｒｏｐｅｎｅｏｖｅｒＨβＺｅｏｌｉｔｅ──ＴｈｅＥｆｆｅｃｔｏｆＲｅａｃｔｉｏｎＣｏｎｄｉｔｉｏｎｓｏｎｔｈｅＤｉｓｔｒｉｂｕｔｉｏｎｏｆＰｒｏｄｕｃｔｓＭＡＪｕｎ，ＳＨＥＮＪｉａｎ－ｐｉｎｇ，ＳＵＮＴ...     

Thermocontrolling ion permeation through binary component membrane composed of crown ether liquid crystal/PVC

In view of the nature of orderness in structure and the mesomorphism in property of liquid crystal, the function of which is further exploited by integrating it with the feature of crown ether. The monoarmed crown ether liquid crystals are successfully applied to the imitation of biomembrane transport. Binary component membrane composed of crown ether liquid crystal and PVC was first developed. Such a novel model of biomimetic membrane is capable of imitating ingeniously the thermocontrolling transport of biomembrane, thus the essential function of liquid crystal in membane transport is more fully exploited. It was suggested, consequently, that the molecules of the crown ether liquid crystal could assemble themselves to form ionic channels, as they exist in mesophase.Of still more significance is that the thermocontrolling transport of ions through the membrane is found to be operative selectively and the permeation of ion is under the direct influence of the thermal turmoil of the crown ether liquid cr     

The effects of alkali metal(Na+,K+) on the exchange degree of Hβ zeolite and the catalytic properties of the alkalized zeolites

The effects of alkali metals (Na+,K+) on the exchange degree of Hβ zeolite under different conditions and the conversion of α(or β)-methylnaphthalene over the alkalized zeolites were studied. The results showed that the H+ of Hβ zeolite is totally replaced by the Na+ of NaCl solution, while partially exchanged by the K+ of KC1 solution, there is an exchange equilibrium between the H+ and K+ for Hβ zeolite (Si/Al=17.23) and the value of equilibrium is 88.39. The exchange degree also increases with increasing the Si/Al of the samples. It was suggested that these resluts are attributed to the electrostatic field in the pore of Hβ zeolite and the nature of zeolite and the properties of alkali metal. The isomerization of α(or β)-methylnaphthalene is the main reaction over the samples and it is more favour on the proper acid-base sites of KHβ zeolite.     

Ferromagnetically coupled heterobinuclear Cu(Ⅱ)-Ln(Ⅲ) complexes with N,N''''-bis(2-aminoethyl)-oxamido dianion as a bridged ligand

Six novel μ-oxamido heterobinuclear complexes, namely Cu(oxae)Ln(Me2bpy)2-(ClO4)3 (Ln=La, Nd, Gd, Tb, Ho, Er), where oxae denotes N, N'-bis(2-aminoethyl)oxamido dian-ion, Me2bpy is 4,4'-dimethyl-2,2'-bipyridyl, have been synthesized and characterized by elemental analyses, IR, conductivity measurements and electronic spectra. The temperature dependence of the magnetic susceptibility of Cu(oxae)Gd(Me2bpy)2(ClO4)3 has been meaured over the range 4-300 K. The least-squares fit of the experimental susceptibilities yielded J - 1.87 cm-1.The observed Gd(Ⅲ)-Cu(Ⅱ) coupling is ferromagnetic. One plausible mechanism that can cause a ferromagnetic coupling between Gd(Ⅲ) and Cu(Ⅱ) is discussed in terms of spin-polarization.     

PS／LDPE共混体系形变机理的TEM研究

ＰＳ／ＬＤＰＥ共混体系形变机理的ＴＥＭ研究徐世爱，江明（复旦大学高分子科学系、聚合物分子工程实验室，上海，２００４３３）沈静姝（中国科学院北京化学所高分子物理开放实验室）关键词形变机理，银纹，透射电镜，共混物在ＰＳ／ＬＤＰＥ共混体系中加入接枝或嵌段共...     

Zn_2Al－PW_（12－n）V_nO_（40）（n＝1～4）的合成与表征

Ｚｎ_２Ａｌ－ＰＷ_（１２－ｎ）Ｖ_ｎＯ_（４０）（ｎ＝１～４）的合成与表征郭军，孙铁，沈剑平，蒋大振闵恩泽（吉林大学化学系，长春，１３００２３）（石油化工科学研究院）关键词Ｐ－Ｗ－Ｖ杂多阴离子，柱撑水滑石，合成同多和杂多阴离子柱撑水滑石（简称ＰＯＭｓ－...