氟化锶／氧化钕催化剂的甲烷氧化偶联性能及其吸附氧物种的原位FTIR光谱研究

氟化锶／氧化钕催化剂的甲烷氧化偶联性能及其吸附氧物种的原位ＦＴＩＲ光谱研究龙瑞强，万惠霖，赖华龙，蔡启瑞（厦门大学化学系固体表面物理化学国家重点实验室，厦门，３６１００５）关键词甲烷氧化偶联，氟化锶／氧化钕，吸附氧物种近年来，甲烷氧化偶联（ＯＣＭ）的...     

Ag/ZrO2催化剂上的1,2-丙二醇选择性气相氧化反应

采用浸渍法制备了一系列Ag/ZrO₂催化剂, 考察了Ag/ZrO₂催化剂对1,2-丙二醇选择性氧化合成丙酮醛反应的催化性能. 实验结果表明: 在原料气配比为V(N₂)∶V(O₂)＝300∶19, n(O₂)/n(alcohol)＝1.2, 反应物液时空速为3.2 g/(g•h), 反应温度为673 K时, 1,2-丙二醇选择性氧化合成丙酮醛反应的转化率为95.7%, 选择性为55.3%, 高于传统电解银催化剂. UV-Vis DRS和XPS的研究结果表明: 在Ag/ZrO₂催化剂上存在大量的Ag^＋和Ag_n^δ＋有利于促进催化活性的提高.     

水热一步法合成Ti-SBA-15分子筛及其催化性能研究

采用钛酸丁酯和乙酰丙酮作用后的产物作为钛的前驱体，水热法一步合成出了 Ti-SBA-15分子筛。通过X射线衍射、N2气吸附脱附、紫外—可见漫反射等表征手段 ，证明在Si/Ti＝50，25，20时，钛原子成功地取代了SBA-15中的硅原子而没有改 变SBA-15高度有序的介孔二维六角结构，其中钛全部以四配位状态存在，而且高度 分散。当Si/Ti＝12．5时，钛的分散度降低，部分钛聚集生成二氧化钛。与用两步 法合成的Ti-SBA-15比较，一步法合成的Ti-SBA-15中钛分散度好，添加量高，对催 化氧化环己烯有较高的催化活性。对一步法和两步法合成Ti-SBA-15的机理以及相 应产物在结构以及催化活性上的差异进行了探讨。     

Forming extremely smooth ZnO thin film on silicon substrates for growth of large and well-aligned ZnO rods with the hydrothermal method

Sol–gel zinc oxide (ZnO) thin films generally have non-uniform stripes. After annealing at high temperatures, these thin films are rough and granular. When ZnO rods are grown on such rough and non-uniform surface with the hydrothermal method, collimation, crystalline structure, and defect density are very poor. Here we explore a method to solve this problem. The ZnO thin film is first coated with an Au layer to prohibit the vertical extension of crystallization during the annealing period. As a result, the surface morphology of ZnO thin film is very flat and uniform after annealing. Afterwards, the ZnO rods are grown on the flat and uniform thin film, which gives rise to ZnO rods with very good collimation and crystalline structure. The extremely flat ZnO thin film even enables the fabrication of patterned ZnO rod arrays with regular shapes through lithography.     

Solid-state syntheses, crystal structures and properties of two novel metal sulfur chlorides—Zn6S5Cl2 and Hg3ZnS2Cl4

Two novel metal sulfur chlorides - Zn₆S₅Cl₂ (1) and Hg₃ZnS₂Cl₄ (2) - were obtained by solid-state reactions and structurally characterized by single-crystal X-ray diffraction. Compound 1 is characteristic of a 1-D tunnel-like structure, which connects to each other to construct a 3-D framework with the chlorine atoms locating at the voids. Compound 2 crystallizes in the acentric space group P6₃mc of the hexagonal system. Compound 2 features a 2-D layered motif, which is composed by the interconnected 12-membered Hg₆S₃Cl₃ rings with chair-like conformation. There are ZnSCl₃ tetrahedra located between the layers, yielding a sandwich-like structure. TG-DTA measurement shows that compound 1 is thermally stable up to 220 °C. Optical absorption spectra reveal the presence of sharp optical gap of 2.71 and 2.65 eV for 1 and 2, respectively.     

Synthesis and characterization of a novel quaternary metal chalcogenide-Hg3ZnSe3Br2

A novel quaternary metal chalcogenide Hg₃ZnSe₃Br₂ (1) was prepared via a solid-state reaction method and structurally characterized by single-crystal X-ray diffraction. Compound 1 crystallizes in the space group P-3 of the hexagonal system with two formula units in a cell: a = 7.383(7) ?, c = 10.924(9) ?, V = 515.6(8) ?³, FW = 1063.84, D _c = 6.852 g/cm³, S = 0.713, ??(MoK _??) = 65.083 mm^?1, F(000) = 884, R = 0.1377 and wR = 0.2720. Compound 1 is characterized by a 2-D layered motif, which is constructed from the interconnected 12-membered Hg₆Br₆ rings with a chair-like conformation.     

Ca2+掺杂铌酸锶钡晶体的光折射变化特性研究

基于Ca²⁺掺杂铌酸锶钡晶体的透射特性,探讨了Ca²⁺在晶体中的电子行为机制，分析了Ca²⁺掺杂而引起的光致折射率变化特性.采用Michelson干涉装置测得了样品折射率随时间变化的特性曲线.实验结果分析表明，适当的Ca²⁺掺杂可以有效改善铌酸锶钡晶体的光折射特性. 关键词： 2+')" href="#">Ca²⁺ 铌酸锶钡 透射率 光折变     

Ca2+掺杂铌酸锶钡晶体的光折射变化特性研究

基于Ca2+掺杂铌酸锶钡晶体的透射特性,探讨了Ca2+在晶体中的电子行为机制,分析了Ca2+掺杂而引起的光致折射率变化特性.采用Michelson干涉装置测得了样品折射率随时间变化的特性曲线.实验结果分析表明,适当的ca2+掺杂可以有效改善铌酸锶钡晶体的光折射特性.     

钾对苯甲酸甲酯加氢催化剂MnO_x/γ-Al_2O_3的修饰作用

采用浸渍法引入不同含量的钾元素对MnO_x/γ-Al_2O_3催化剂进行了改性,在 常压固定床反应器上研究了经不同含量修饰的催化剂对苯甲酸甲酯加氢生成苯甲醛 反应的影响。通过XRD,XPS,NH_3-TPD,BET,IR等手段对催化剂进行了表征,结 果表明：修饰后的催化剂并没有改变锰的价态,引入的钾和Al_2O_3发生了作用, 形成了新的晶相K_2Al_2O_4,改性后的催化剂减弱了催化剂表面的酸强度,并且减 少了酸中心数。催化剂表面具有中等强度的L酸中心可以有效抑制副产物甲苯和苄 基甲醚的生成,显著地提高了苯甲醛的选择性。     

[N-ethyl-4,4'-bipyridinium][ZnX_4](X = Cl or Br) with N-ethyl-4,4'-bipyridinium Generated In Situ:Syntheses,Structures, Fluorescence and TDDFT Calculations

Two new zinc bipyridinium compounds, [N-ethyl-4,4′-bipyridinium][ZnX4](X = Cl(1) or Br(2)) with N-ethyl-4,4′-bipyridinium generated in situ, have been synthesized through solvothermal reactions and structurally characterized by single-crystal X-ray diffraction analyses. Both compounds are isostructural and crystallize in the P21/c space group of monoclinic system. Compound 1: a = 8.4397(5), b = 21.988(1), c = 8.8777(5) , β = 106.490(1)°, V = 1579.7(2) 3, C12H15Cl4N2 Zn, Mr = 394.43, Z = 4, Dc = 1.658 g/cm3, S = 1.068, μ(MoKα) = 2.218 mm-1, F(000) = 796, R = 0.0295 and wR = 0.0766. Compound 2: a = 8.4154(6), b = 22.844(2), c = 9.0308(7) , β = 106.026(1)°, V = 1668.6(2) 3, C12H15Br4N2 Zn, Mr = 572.27, Z = 4, Dc = 2.278 g/cm3, S = 1.033, μ(MoKα) = 11.038 mm-1, F(000) = 1084, R = 0.0427 and wR = 0.1175. Both of them are characteristic of an isolated structure with the zinc atoms locating at a tetrahedral environment. In both compounds, the N-ethyl-4,4′-bipyridinium2+ cations and ZnX42– anions interconnect together via hydrogen bonding interactions to construct a three-dimensional(3-D) supramolecular framework. Fluorescent studies reveal that both compounds exhibit a strong emission in the green region. In combination with the theoretical calculations, we can draw a conclusion that the emissions should result from ligand-toligand charge-transfer(LLCT) transition.