三维配位聚合物(DETA)_4Na[Na(H_5P_4Mo_6O_(31))_2]·8H_2O的水热合成、结构及电化学性质

Hydrothermal synthesis,structure and electrochemical properties of three-dimensional complex:(DETA)_4Na[Na(H_5P_4Mo_6O_(31))_2]·8H_2O

通过水热法合成了一维链状的磷钼氧酸盐(DETA)4Na[Na(H5P4Mo6O31)2]·8H2O(DETA=Diethylenetriamine),采用X-射线单晶衍射结构分析,元素分析和红外光谱等表征.该磷钼氧酸盐属于三斜晶系,空间群是P-1,晶胞参数a=1.243 4(3)nm,b=1.261 0(3)nm,c=1.307 9(3)nm,α=85.418(3)°,β=73.399(2)°,γ=82.175(3)°,V=1.945 0(8)nm3,F(000)=1 462,Z=2.标题化合物的结构是由[Na(H5P4Mo6O31)2]簇单元,二亚乙基三胺阳离子和结晶水分子组成.另外,[Na(H5P4Mo6O31)2]簇由钠离子连接形成了一维的链结构.一维链结构又由于二亚乙基三胺阳离子和结晶水分子形成的氢键进一步连接三维超分子结构.用标题化合物修饰的碳糊电极(APM-CPE)对AA氧化有很好的电催化活性.

A 1D chain polyoxomolybdophosphate network, （DETA）4Na[Na（HsP4Mo6Oal）2] ~ 8H20 （DETA=Diethylenetriamine）, has been synthesized by hydrothermal and characterized by elemental analyses, IR spectrum, and single-crystal X-ray diffraction analysis, crystallizes triclinic system, space group P-1 with a=l. 243 4（3） nm, b=l. 261 0（3） nm, c=l. 307 9（3） nm, a=85. 418（3）°, β= 73. 399（2）°,γ=82. 175（3）°, V=1.945 0（8） nm3, F（000）=I 462, Z=2. The structure of the title compound consists of [Na（Ha P4 Mo60al ）2 ] cluster unit, diethylenetriamine cations and lattice water molecules. In addition, the [Na（ Hs P4 Mo60al ）e ] clusters are bridged together into one-dimensional chain by sodium ions. And the one-dimensional strings are further connected into a three-dimensional supramolecular structure through hydrogen bonding involving lattice water molecules and the diethyle- netriamine cations. The bulk-modified carbon paste electrode（APM-CPE） using this compound as modifier shows a good electrocatalytic activity toward the oxidation of ascorbic acid（AA）.