Fe(Ⅲ)与两种4-羟基吡啶二酸形成的配合物的合成与晶体结构

0 引言 最近,我们对2,6-吡啶二酸的衍生物4-羟基-2,6-吡啶二酸(2,6-HAD)的配合物进行了一系列的研究,结果发现2,6-HAD是一个优良的刚性配体,其配位方式种类繁多,特别是配体上的4位羟基,既具有较强的配位能力[1],又可以形成分子间氢键[2,3],影响和控制配合物的超分子结构,4-羟基-2,6-吡啶二酸不仅能与过渡金属、镧系金属离子分别形成稳定的配合物[1-3],而且能同时与稀土和过渡金属形成具有纳米孔穴的混金属配合物,这些配合物在磁性、光学等方面都显示出优异的性能[4].     

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.     

水热反萃法制备纳米α-Fe2-O3

氧化铁;环烷酸;制备;水热反萃法制备纳米α-Fe2-O3     

Pt/Al2O3蜂窝状催化剂上NO选择性催化还原反应动力学研究

采用多次涂层和浸渍法制备了蜂窝状Pt/Al2O3催化剂，并在高空速和大气体流量条件下对无梯度循环式反应器和积分反应器上催化剂的活性进行了比较。同时采用循环式反应器对动力学数据进行了测定。根据Langmuir-Hinshelwood模型和实验结果，推测了NO-C3H6-O2体系的SCR反应机理，并导出了NO和C3H6反应速率的数学表达式。据此所计算的理论模拟值能够与实验值很好地吻合。实验结果表明，氧气浓度对NO和C3H6的反应速率有明显的影响，二者均随着氧浓度c (O2)的增加达到峰值，再增加氧气浓度时，C3H6的反应速率r(C3H6)保持不变，而NO反应速率r (NO)却下降，而且下降的程度随着温度的升高而加剧。同时，随着氧气浓度增加，r (NO)达到最大值时的温度亦随之下降。     

互通多孔碳/二氧化锰纳米复合材料的原位水热合成及电化学性能

以互通多孔碳（IPC）为载体，水热条件下在碳表面原位反应生成纳米结构的二氧化锰（MnO₂），制备互通多孔碳/二氧化锰纳米（IPC/MnO₂）复合电极材料. 采用扫描电镜（SEM），透射电镜（TEM），X射线衍射（XRD），热重分析（TGA）对其结构进行表征；采用循环伏安法、恒流充放电和交流阻抗对其电化学性能进行研究. 结果表明：生成的MnO₂均匀地负载在碳的表面，形成多层次结构，并且随着温度的升高IPC表面负载的MnO₂由纳米颗粒变为纳米片状结构；MnO₂纳米片具有典型的K-Birnessite 型晶体结构；复合物中MnO₂的含量约为34%（w）. 在100 ℃制备的IPC/MnO₂复合材料在三电极系统中最高比电容达到了411 F·g^-1；随着反应温度的升高,比容量先增长后基本保持不变. 以IPC/MnO₂为正极，活性炭（AC）为负极，1 mol·L^-1 Na₂SO₄溶液为电解液组装成IPC/MnO₂//AC 混合超级电容器，发现IPC/MnO₂电极的电容器其电位窗口从1 V扩展到1.8 V，容量可达86F·g^-1，且表现出良好的电容特性和大电流放电性能.     

烯胺酮与烯胺酯的交叉缩合反应及自缩合反应的区域选择性研究

烯胺酮与烯胺酯以(3C+3C)缩合反应形成多取代芳环化合物,具有区域选择性。用波谱和 X-射线衍射技术确定了产物的结构,讨论了反应机理。     

Structure, bonding, and reactivity of Ti and Zr amidate complexes: DFT and X-ray crystallographic studies

Easily prepared and highly modular organic amide proligands have been used to synthesize a series of new bis(amidate)-bis(amido) Ti and Zr complexes via protonolysis. These complexes have been structurally characterized by NMR spectroscopy and X-ray crystallography. The solid-state molecular structures of these complexes indicate that the amidate ligands bind to the metal centers in an exclusively bidentate fashion, resulting in discrete monomeric species. Geometric isomerism in these species is highly dependent upon the steric characteristics of the proligands utilized in the synthesis. In solution, these complexes are observed to isomerize on the NMR time scale, with one isomer being predominant. Bonding in the bis(amidate)-bis(amido) complexes was investigated by DFT calculations. The geometric isomers predicted by theory matched the experimentally observed results, within experimental error. The orbitals associated with amidate-metal bonding are energetically well below the frontier orbitals. The HOMO in these complexes is a pi orbital associated with amido ligand-to-metal bonding character, while the LUMO in all cases is a vacant d orbital on the metal center.     

分散固相萃取结合气相色谱-高分辨质谱快速筛查酱油中多种氯丙醇

建立了酱油中1，3-二氯-2-丙醇、2，3-二氯-1-丙醇、3-氯-1，2-丙二醇和2-氯-1，3-丙二醇的分散固相萃取-气相色谱-高分辨质谱快速筛查检测方法。样品采用乙酸乙酯提取，提取液浓缩后经N-丙基乙二胺净化，气相色谱-高分辨质谱测定，内标法定量。结果表明，该方法对于酱油中4种氯丙醇的定量限为0.5~10 μg/kg。在3个浓度水平下的加标回收率为78%~103%；相对标准偏差均不大于8.8%。该方法快速、简便、准确、灵敏，可作为酱油中4种氯丙醇的有效检测方法。     

利用高炉水淬渣制备(Ca/Y)-α-Sialon陶瓷的组织与性能

以高炉水淬渣合成的Ca-α-Sialon粉体为原料采用无压烧结技术制备了（Ca/Y）-α-Sialon陶瓷。通过用排水法、三点弯曲实验法、金相显微镜法、XRD法等手段研究了（Ca/Y）-α-Sialon陶瓷的烧结致密化过程、材料的力学性能、显微组织、相组成和材料的断裂特征。结果表明,适量的Y2O3促进材料的烧结致密化和提高材料的力学性能,但Y2O3过量（大于10%）时对材料的烧结和力学性能不利。掺杂Y^3＋的（Ca/Y）-α-Sialon呈柱状晶,随着Y2O3含量的增加和烧结温度的提高,（Ca/Y）-α-Sialon呈柱状晶出现粗化和等轴化。含10%Y2O3的材料在1700℃烧结时可获得较高的力学性能。     

Synthesis and Ionic Conductivity of Network Polymer Electrolytes with Internal Plasticizers

Network polymer electrolytes with free oligo(oxyethylene) chains as internal plasticizers were prepared by cross-linking poly(ethylene glycol) acrylates. The effects of salt concentration and properties of internal plasticizers on ionic conductivity were studied.