铝柱撑二硫化钼的制备及其催化氧化性质

本文采用单分子层技术将聚合羟基铝簇离子嵌入到二硫化钼板层间，得到层间距为1.481至1.519 nm的柱撑二硫化钼复合材料。XRD、DSC等研究表明，柱化液的滴加浓度越稀、柱撑反应体系中Al∶MoS₂物质的量之比越小越有利于获得层间距较大的柱撑材料。与原料2H-MoS₂相比，柱撑材料的层间距增大，颗粒度变小，比表面积增加。在氧气条件下，对Na₂S的催化氧化实验表明，柱撑材料较原料2H-MoS₂的催化氧化活性提高3～4倍，且光催化活性大于催化活性。这与柱撑材料的比表面积增加所导致催化活性部位的增多，以及光致电子-空穴对的产生有关。     

Hydrothermal Synthesis and Structure of a Novel Binuclear Molybdenum Complex with Oxalate Ligand,(enH2){NH4[Co(en)3][Mo2O7(C2O4)]}2·2H2O

The title complex (enH2){NH4[Co(en)3][Mo2O7(C2O4)]}2·2H2O (C18H70Co2Mo4- N16O24, Mr = 1396.52) was obtained under hydrothermal conditions and its crystal structure has been determined by single-crystal X-ray diffraction. It crystallizes in the monoclinic system, space group P21/c with a = 17.8023(8), b = 7.7527(4), c = 16.9781(4)A,β= 103.878(7)°, V = 2274.8(2) A3, Dc = 2.039 g/cm3, Z = 2,μ(MoKα) = 1.878 mm-1 and F(000) = 1408. The final R = 0.0410 and Wr = 0.1070 for 4065 observed reflections with I≥2σ(I). The crystal structure is composed of bi- nuclear [Mo2O7(C2O4)]4- anions, complex [Co(en)3]2+ cations, protonated ethylenediamine cations, ammonium cations and crystal water molecules, which are held together into a three-dimensional network via hydrogen-bonding interactions. The binuclear structure of [Mo2O7(C2O4)]4- consist of one MoO4 and one MoO6 octahedra through sharing a bridging oxygen atom, where the oxalate ligand acts as a bidentate ligand coordinating to the octahedral molybdenum atom though two deprotonated corboxylate groups.     

含钴(Ⅱ)配阳离子的MoS2基嵌入化合物

本文测量了表面ζ电位随pH值的变化关系，表明MoS₂单分子层表面吸附的是OH^-离子，其等电点在pH=2附近。在pH=5～10范围内，ζ电位在-22到-24 mV之间，较为稳定。在pH=7.2条件下，利用MoS₂单分子层与钴(Ⅱ)配位阳离子基团反应合成了3个嵌入化合物[Co(H₂O)_z]_y/2MoS₂、[Co(bpy)₃]_y/2MoS₂和[Co(phen)₃]_y/2MoS₂。X-射线衍射、元素分析和热重分析研究表明前一个化合物中每10个{MoS₂}单元约嵌入一个水合钴离子，层间距增大了0.893nm，水合钴离子在基体层间按双层错开排列。后两个化合物中每20个{MoS₂}单元约嵌入一个钴有机配阳离子，层间距分别增大了0.953和1.018 nm，配位阳离子则单层排列于MoS₂基体层间，[Co(bpy)₃]²⁺和[Co(phen)₃]²⁺离子中CoN₆配位八面体的三次对称轴近于垂直于MoS₂基体层板。