钒电池电解液体积变化规律研究

研究了钒电池在使用阳离子交换膜稳定运行过程中电解液体积的变化情况, 分析了影响因素, 并总结了变化规律. 离子的电迁移使电解液体积随充放电容量的变化线性改变, 充电过程正极电解液体积线性减小, 负极电解液体积线性增大; 放电过程反之. 多次充放电循环过程中, 钒离子的净渗透方向是由负极到正极, 水的净变化方向与钒离子相同, 最终使得多次循环过程正极电解液的体积逐渐增加.     

5,10,15,20—四（对—乙酯苯基）卟啉LB膜的结构

对卟啉类化合物LB膜的结构、电性质和气敏性的研究已见报道。本文利用膜天平和UV-Vis分光光度计研究了标题化合物在气-液界面上的成膜特性、分子间相互作用和LB膜的结构。5,10,15,20-四(对-乙酯苯基)卟啉(TPEPP)由5,10,15,20-四(对-氰苯基)卟啉和乙醇酯化得到。元素分析测定值与计算值相符。λ(CHCl_3,nm):421,515,550,590,645;ν(KBr压     

Distinct Hydrogen-bonded M^Ⅱ（H2O）8 Clusters as Second Building Units for 1-D, 2-D and 3-D Supramolecular Architectures （M = Cobalt and Nickel）

Two mononuclear metal-organic complexes, [Co（Hmpdc）2（H2O）4]·4H2O 1 and [Ni（Hfmpdc）2（H2O）4]·6H2O 2, were prepared from 2,6-dimethylpyridine-3,5-dicarboxylic acid （Hzmpdc） and 4-furyl-2,6-dimethylpyridine-3,5-dicarboxylic acid （H2fmpdc） with M（NO3）2 salts, respectively, and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectroscopy, and photoluminescent measurement. Complex 1 crystallizes in triclinic, space group P1 with a = 7.634（5）, b = 8.695（5）, c = 10.757（6）A, α = 69.647（7）, β = 69.957（8）, γ = 83.733（7）°, V = 628.9（7）A^3, Dc = 1. 561 g/cm^3,μ（MoKa） = 0.763 mm^-1, F（000） = 309, Z = 1, the final R = 0.0553 and wR = 0.1469 for 1909 observed reflections （Ⅰ 〉 2σ（Ⅰ））. Complex 2 crystallizes in monoclinic, space group P21/n with a = 9.5934（16）, b = 12.422（2）, c = 14.826（3） A, β = 105.201（2）°, V = 1705.0（5）A3, Dc = 1. 479 g/cm^3,μ（MoKa） = 0.655 mm^-1, F（000） = 796, Z = 2, the final R= 0.0351 and wR = 0.0889 for 2387 obsevved reflections （Ⅰ 〉 2σ（Ⅰ））. In the crystal structures of 1 and 2, diverse supramolecular motifs from 1-D chains/ladders to 3-D networks are constructed from corresponding distinct [M^Ⅱ（H2O）8] ion clusters as the second building units, respectively. The solid state compounds of 1 and 2 show similar photoluminescent spectra with emission maximum at ca.     

一种新颖的二维4f-3d-5d多金属-异烟酸配合物的合成、晶体结构和磁性研究

通过水热方法合成了一种新颖的异金属金属-异烟酸无机-有机杂化体[Zn0.5(H2O)]{(Hg2Cl5)[Er(C6NO2H4)3(H2O)2]}(HgCl2)·0.5CH3OH·0.5H2O (1)并对其进行了单晶X-射线衍射结构表征。该化合物是首例4f-3d-5d多金属-异烟酸配合物。化合物1属于单斜晶系C2/c空间群,每个单胞中有8个分子,晶体学参数为：a = 34.165(4) Å,b = 9.4692(8) Å,c = 24.575(3) Å,β = 115.090(5)°,V = 7200(1) Å3,C18.50H21Cl7ErHg3N3O10Zn0.50,Mr = 1495.25,Dc = 2.759 g/cm3,T = 293(2) K,μ(MoKα) = 15.954 mm-1,F(000) = 5400, R1/wR2 = 0.0561/0.0909,共有6468个独立衍射点,其中[I > 2σ(I)]的有3157个。该化合物具有新颖的二维{(Hg2Cl5)[Er(C6NO2H4)3(H2O)2]}层状结构,由Hg2Cl5–连接[Er(C6NO2H4)3(H2O)2]链形成。该二维层和氯化汞及结晶水之间通过氢键形成三维结构,甲醇分子和水合锌离子位于该三维结构的空隙中。对化合物1的磁性测试显示该化合物具有反铁磁作用。     

微波辅助萃取-高效液相色谱法检测动物组织和牛奶中喹诺酮及非甾体类化合物

本文建立了一种快速的微薄辅助萃取-高效液相色谱法分离检测羊肝、牛肉和牛奶样品中三种喹诺酮类药物（氟罗沙星、洛美沙星和斯帕沙星）和两种非甾类化合物(酮洛芬和布洛芬)的方法。并对微波辅助萃取条件利用正交试验进行了优化：萃取温度为4℃、萃取时间为6min、萃取溶剂为乙腈、萃取溶剂体积为10mL。在浓度范围为0.25—0.75 μg•g－1时各待测物的三种不同水平的添加回收率在60.0%到107%之间,并获得较好的精确度（RSD＜11%）。     

New conversion of Friendlnder reaction of 3-amino-1H-benzo[f]chromene-2-carbonitriles with cyclohexanone

Two different skeletons of heterocyclic compounds,quinoline and quinazolinone analogs could be obtained by a novel one-pot synthesis from substituted 3-amino-1 H-benzo[f]chromene-2-carbonitrile derivatives and cyclohexanone in DMF in the catalyst of anhydrous zinc chloride under reflux.A plausible mechanism was proposed.     

微波水热两步法合成高可见光响应Ag2S/ZnO及其光催化性能、机理

在不同的制备条件下,通过微波水热两步法获得了一系列Ag₂S/ZnO光催化剂,采用X射线粉末衍射(XRD)、X射线光电子能谱(XPS)、紫外-可见漫反射吸收光谱(UV-Vis/DRS)、扫描电子显微镜(SEM)和N₂吸附-脱附等测试手段对产物结构和形貌进行了表征。结果表明,产物以六方纤锌矿ZnO为主,其晶型结构并未随着反应温度和Ag₂S物质的量的增加而改变。Ag₂S的引入显著增强了光催化剂在可见光区的吸收,使吸收边带发生红移,同时抑制了ZnO(001)晶面的生长。另外,所得产物的形貌随着Ag₂S物质的量的增加从爆米花状转变为少量的柱体颗粒,且BET比表面积经过复合后明显减小。以罗丹明B为目标降解物,研究并比较了一系列Ag₂S/ZnO光催化剂对罗丹明B的光降解性能。结果表明,n_Ag2S/n_ZnO=1:10时,光催化剂在紫外光、可见光和模拟日光的照射下具有最好的光催化效果,优于目前应用最广泛的市售P25。另外,所制备的光催化材料Ag₂S/ZnO经4次循环使用后,其降解效率没有明显下降,表明该催化材料具有一定的光催化稳定性。经捕获实验研究发现,在Ag₂S/ZnO的光催化反应中空穴起主要作用,并根据绝对电负性估算了复合材料Ag₂S/ZnO的能带位置,据此提出了可能的光催化反应机理。     

Highly Dense Isolated Metal Atom Catalytic Sites: Dynamic Formation and In Situ Observations

Atomically dispersed noble‐metal catalysts with highly dense active sites are promising materials with which to maximise metal efficiency and to enhance catalytic performance; however, their fabrication remains challenging because metal atoms are prone to sintering, especially at a high metal loading. A dynamic process of formation of isolated metal atom catalytic sites on the surface of the support, which was achieved starting from silver nanoparticles by using a thermal surface‐mediated diffusion method, was observed directly by using in situ electron microscopy and in situ synchrotron X‐ray diffraction. A combination of electron microscopy images with X‐ray absorption spectra demonstrated that the silver atoms were anchored on five‐fold oxygen‐terminated cavities on the surface of the support to form highly dense isolated metal active sites, leading to excellent reactivity in catalytic oxidation at low temperature. This work provides a general strategy for designing atomically dispersed noble‐metal catalysts with highly dense active sites.