V_2O_5/C催化氧化乙二醛制备乙醛酸

利用等体积浸渍法制备了V2O5/C催化剂,并应用于乙二醛的液相氧化反应,采用XRD、TEM手段对催化剂进行了物化性质表征.结果表明,V2O5/C对乙二醛的氧化表现出较高的催化活性和乙醛酸选择性,反应10h,乙二醛的转化率达29.2%,乙醛酸得率13.6%.与贵金属Pd-Bi/C催化剂相比,V2O5/C催化剂的稳定性和重复使用效果都比较好.     

双核配合物[Cu2(TS)(H2O)]·CH3OH的自组装制备和晶体结构

The binuclear complex [Cu₂(TS)(H₂O)]·CH₃OH, where TS denotes the binucleating ligand derived from the schiff base N,N′-bis(3-carboxylsalidene)trimethylenediamine, was obtained from the self-decomposition of mononuclear complex Na₂CuTS·H₂O. It crystallizes in the monoclinic system, space group P2₁/c. The lattice parameters are a=11.935(2)?,b=15.667(3)?,c=11.621(2)?,β=111.60(3)°,V=2020.2(7)?³, Z=4 with R=0.0467. The structure is made of binuclear units, in which two copper atoms are bridged by two phenolic oxygen atoms. The “inside”copper atom is coordinated by two nitrogens, two phenolic oxygens in a planar coordi-nation site, the copper atom deviates from the mean plane by 0.47?. The “outside” copper atom is five coordinated by two phenolic oxygen atoms、two equatorial carboxyl oxygen atoms and one axial water oxygen atom in a distorted tetragonal cone site, the copper atom is pulled out of the equatorial plane by 0.46?.     

On the Criteria of Instability for Electrochemical Systems

Both cyclic-voltammetry-based and impedance-based experimental criteria that have been developed recently for the oscillatory electrochemical systems are critically appraised with two typical categories of oscillators.Consistent conclusions can be drawn by the two criteria for the category of oscillators that involve the coupling of charge transfer mainly with surface steps(e.g.ad-and desorption)such as in the electrooxidation of C1 organic molecules.Whereas,impedance-based criterion is not applicable to the category of oscillators that involve the coupling of charge transfer mainly with mass transfer(e.g.diffusion and convection) such as in the Fe(CN)6^3- reduction accompanying periodic hydrogen evolution.The reason is that the negative impedance cannot include the feedback information of convection mass transfer induced by the hydrogen evolution.However,both positive and negative nonlinear feedbacks,i.e., the diffusion-limited depletion and convection-enhanced replenishment of the Fe(CN)6^3- surface concentration,that coexist between the bistability,i.e.,Fe(CN)6^3- reduction with and without hydrogen evolution at lower and higher potential sides respectively,are all reflected in the crossed cyclic voltammogram(CCV).It can be concluded that the voltammetry-based criterion(in time domain)is more intuitive,less time-consuming and has a wider range of applications than the impedancebased one (in frequency domain).     

激光光散射研究丙烯酰胺-二甲基二烯丙基氯化铵共聚物的溶液行为

用激光光散射技术表征了阳离子含量受控的丙烯酰胺 二甲基二烯丙基氯化铵共聚物 (简称P(AM DMDAAC) )在 0 1mol LNaCl溶液中的基本参数和溶液行为 .表观基本参数 : Mw ,app =5 0 4× 10 5g·mol- 1 、app =39 9nm和A2 ,APP =1 5× 10 - 4cm3·mol·g- 2 .动态光散射研究结果表明 ,扩散系数Dt 与角度、浓度皆呈非线性依赖关系 ,当C >C 或在较大的散射角域 ,Dt 偏离线性关系所预示的理论值而向减小的方向发展 ,表明存在缔合物 ;流体力学半径Rh 分布有大、小两个范围 ,并随温度升高向小尺寸方向发展 ,证明了体系中存在缔合行为以及升温的解缔合作用 .在一定条件下 ,“亚稳定性”的存在有力地旁证了体系的缔合行为     

Synthesis, crystal structure and characterization of a 2-D network organic-inorganic hybrid polymer with [α-BW12O40]5- as building blocks

A two-dimensional network compound [Ce(DMF)4(H2O)][α-BW12O40]·H2O·(HDMA)2 (HDMA = protoned dimethylamine, DMF = N,N-dimethylformamide) was synthesized from α-H5BW12O40·nH2O, Ce(NO3)3·6H2O and DMF and characterized by IR, UV spectra and TG-DTA. The result of the X-ray single crystal diffraction indicates that the crystal is monoclinic, space group P21/n, with unit cell dimensional: a = 1.1983(3), b = 2.4216(5), c = 1.9517(4) nm, β = 92.91(3)°, Z = 4, R1 = 0.07710, wR2 = 0.1416. Structural analysis indicates that every [Ce(DMF)4(H2O)]3-building block is surrounded by three adjacent [α-BW12O40]5-polyanions, meanwhile, every [α-BW12O40]5-polyanion interconnects with three neighboring [Ce(DMF)4(H2O)]3+ subunits, by making use of which two-dimensional network structure can be constructed. The result of thermogravimetric analysis manifests that the title compound has two-stage weight loss and the decomposition temperature of the title polyanionic framework is 560℃. The electrochemical analysis shows the title polyanion has three-step redox processes in the pH = 4-7 media.     

A Mild and Efficient Deprotection of Geminal Diacetates Catalyzed by FeCl3 ·6H2O in Ionic Liquid

The selective deprotection of geminal diacetates promoted by FeCl3·6H2O in the ionic liquid [bmim] [BF4] canbe efficiently achieved in good yields. The ionic liquid and the catalyst can be recycled easily and the process is car ried out under mild conditions.     

The electrooxidation behavior of bilirubin in DMF and DMF + H_2O mixed solvent

The electrooxidation of Bilirubin (BR) in N,N'-dimethylformamide (DMF) and DMF + H_2O mixed solvent is investigated by voltammetry techniques, in situ rapid scan thin layer spectroelectrochemistry and in situ ESR spectroscopy. The data reveal that the oxidation process of BR undergoes many stages, which are all sped up by the introduction of water. The species of bilirubin taking part in the reaction is found to be changed from BR in DMF into BR' in the mixed solvents and the anodic peak potential is shifted correspondingly from +0.58 V to +0.026-+0.35 V (vs. Ag/AgCl, 1.0 M KCl). Free radicals and the dimerization of them are observed during the oxidation.     

Anderson-B-型多金属氧酸盐[Co(2,2''-bipy)3]H-[Al(OH)6(Mo6O18)]·5H2O的合成及晶体结构

以AlCl3·6H2O、Na2MoO4·2H2O、CoCl2·6H2O和2,2'-联吡啶为主要原料合成了Anderson-B-型多金属氧酸盐[Co(2,2'-bipy)3]H[Al(OH)6(Mo6O18)]·5H2O,进行了红外光谱、紫外光谱、差热分析和单晶结构测定.晶体学测定结果表明,化合物属于三斜晶系,Pi空间群,晶胞参数:a=1.216 0(2),b=1.221 5(2),c=1.780 0(4)nm,α=86.83(3)°,β=88.76(3)°,γ=89.82(3)°,V=2.639 4(9)nm3,Z=2,R1=0.079 4,wR2=0.176 6.化合物结构分析表明,在晶体学上,标题化合物分子是由1个[Co(2,2'-bipy)3]2+配阳离子,1个H+离子,2个1/2[Al(OH)6(Mo6O18)]3-多阴离子和5个结晶水分子组成.多阴离子[Al(OH)6(Mo6-O18)]3-借助水分子和金属配离子通过超分子作用形成二维网状结构,网状结构之间又借助超分子作用形成三维无限伸展结构.差热分析表明,标题化合物的失重过程分为2步,多阴离子骨架破坏温度为547.5℃.     

烯烃在HZSM-5分子筛上原位芳构化反应的研究

烯烃在ZSM-5分子筛上转化成芳烃的反应是一个非常复杂的反应,既包括聚合裂解反应,又包括氢转移、脱氢环化反应,同时也包括烷基转移和脱烷基等反应,对于这一复杂反应的机理研究较少.Vedrine等人[1]认为烯烃首先在酸性位上通过氢转移生成戊二烯正碳离子,接着环化以及扩环反应生成     

Hybrid Tungstocuprate [Cu(2,2'-bpy)3]2H4[CuW12O40]·6H2O Based on Keggin Polyoxoanion [CuW12O40]6-with CuⅡas Heteroatom

A novel hybrid tungstocuprate(Ⅱ) [Cu(2,2'-bpy)3]2H4[CuW12O40]·6H2O(2,2'-bpy=2,2'-bipyridine) was synthesized via hydrothermal method and characterized using elemental analyses, IR, UV, XPS, TG-DSC, EPR, and X-ray single crystal diffraction. The structural analysis shows that the complex consists of an unusual Keggin-type polyoxoanion [CuW12O40]6- and a pair of chiral complex cations [Cu(2,2'-bpy)3] together with four protons and six crystallization water molecules, and the Keggin polyoxoanion is connected with [Cu(2,2'-bpy)3] via multiple C-H…O hydrogen bonds resulting in a dimer.