基于H_(3)PW_(12)O_(40)·xH_(2)O和3,5-二氨基-1,2,4-三氮唑的POMOF的合成、表征及催化氧化碘离子性能  

POMOF based on H_(3)PW_(12)O_(40)·xH_(2)O and 3,5-diamino-1,2,4-triazole:Synthesis,characterization,and catalytic oxidation performance for iodine ion

作　　者：邱双艳 郭军[1,2] 张丹 卢林 张以菊 张太文 QIU Shuang-Yan;GUO Jun;ZHANG Dan;LU Lin;ZHANG Yi-Ju;ZHANG Tai-Wen(School of Chemistry and Materials Science,Guizhou Normal University,Guiyang 550001,China;State Key Laboratory for Efficient Utilization of Medium and Low Grade Phosphate Rock and Its Associated Resources,Wengfu(Group)Co.,Ltd.,Guiyang 550014,China)

机构地区：[1]贵州师范大学化学与材料科学学院,贵阳550001 [2]瓮福(集团)有限责任公司中低品位磷矿及其共伴生资源高效利用国家重点实验室,贵阳550014

出　　处：《无机化学学报》2023年第11期2113-2120,共8页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.21862005);贵州省科技厅计划项目(黔合基础[2019]1457,黔科合支撑[2019]2835,黔科合平台人才[2018]5769);贵州省教育厅青年科技人才成长项目(黔科合KY字[2018]126)资助。

摘　　要：采用水热法合成了一例结构新颖且罕见的Keggin型多金属氧酸盐基金属有机骨架化合物,即[Cu_(4)(3,5-datrz)4][PW^(Ⅵ)_(9)W^(Ⅴ)_(3)O_(39)]·H_(2)O(1),其中3,5-datrz=3,5-二氨基-1,2,4-三氮唑,并通过单晶X射线衍射、傅里叶变换红外光谱、热重分析、粉末X射线衍射和元素分析进行了表征。单晶X射线衍射分析表明:化合物1属于单斜晶系,空间群为C2/c,不对称结构包含2个Cu^(+)、2个3,5-datrz配体、0.5个Keggin型磷钨酸阴离子和1个水分子,除结晶水外各组分之间通过共价键连接成Keggin型多金属氧酸盐基金属有机骨架化合物。以化合物1为非均相催化剂,在温度为55℃时催化H_(2)O_(2)氧化碘离子反应。结果表明,1催化下的碘单质生成速率为6.11×10^(-7)mol·L^(-1)·s^(-1),且重复使用次数达到6次时转化率仍能高达99.6%。A novel and rare case of Keggin-type polyoxometalate-based metal-organic framework compound was synthesized by solvothermal method,namely[Cu_(4)(3,5-datrz)4][PW^(Ⅵ)_(9)W^(Ⅴ)_(3)O_(39)]·H_(2)O(1)(3,5-datrz=3,5-diamino-1,2,4-triazole).Compound 1 was characterized by single-crystal X-ray diffraction,Fourier transform infrared spectroscopy,Thermogravimetric analysis,powder X-ray diffraction,and elemental analysis.The single-crystal X-ray diffraction analysis reveals that compound 1 crystallizes in the monoclinic system with space group C2/c.The asymmetric unit contains two Cu^(+)ions,two 3,5-datrz ligands,one-half of Keggin-type phosphotungstic acid anions,and one water molecule.Except for lattice water,the components are linked by covalent bonding to form Keggin-type polyoxometalate-based metal-organic framework compounds.Compound 1 was used as a heterogeneous catalyst to catalyze the oxidation of iodine ions by H_(2)O_(2)at a temperature of 55℃,and the study showed that the variation of iodine generation by compound 1 was 6.11×10^(-7) mol·L^(-1)·s^(-1),and the conversion rate could still reach as high as 99.6%when it was reused six times.CCDC:2221643.

关 键 词：多金属氧酸盐 金属有机骨架 晶体结构 催化性能 

分 类 号：O614.121[理学—无机化学] O614.613[理学—化学]