（C5H7N2O2）4（SiMo12O40）的合成、结构及催化氧化碘离子研究
收稿日期: 2020-11-05
网络出版日期: 2021-09-08
基金资助
国家自然科学基金项目(21862005);贵州省科技厅计划项目(黔科合LH字[2017]7336);贵州省科技厅计划项目(黔合基础[2019]1457);贵州省科技厅计划项目(黔科合支撑[2019]2835);贵州省科技厅计划项目(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(黔教合KY字[2018]126);中低品位磷矿及其共伴生资源高效利用国家重点实验室开放课题项目(WFKF2017-03)
Study on synthesis,structure and catalytic iodide oxidation of （C5H7N2O2）4（SiMo12O40）
Received date: 2020-11-05
Online published: 2021-09-08
采用常规水溶液法合成了一种新型的有机-无机杂化多金属氧酸盐（C5H7N2O2）4（SiMo12O40）（简称SiMo-12）。采用红外光谱（IR）、热重分析（TG）、单晶和粉末X射线衍射（XRD）、元素分析等对SiMo-12进行了表征。以过氧化氢为氧化剂,运用SiMo-12催化碘离子氧化,考察了催化剂用量、氧化剂用量、pH、温度等因素对反应速率的影响。结果表明：该化合物属三斜晶系,P-1空间群,晶胞参数a=1.097 58（4） nm、b=1.144 88（4） nm、c=1.252 66（4） nm、α=64.665（1）°、β=64.804（1）°、γ=83.441（1）°、V=1.282 89（8） nm3、Z=1、R=0.034 0、wR2=0.079 9。化合物由4个1-咪唑乙酸和一个经典的Keggin型[SiMo12O40]4-单元组成,有机配体和多金属氧酸阴离子之间通过静电作用、质子转移以及氢键作用沿x轴形成一维链,链与链之间相互平行形成平行于xy面的二维层,层与层之间再通过氢键连接而得到三维网状结构。SiMo-12在催化碘离子氧化中表现出较为优异的催化活性,在c（SiMo-12）=2.0×10-4 mol/L、c（过氧化氢）=2.0×10-3 mol/L、pH=1.4、50 ℃条件下反应速率达到2.641 6×10-5 mol/（L·s）,比未加催化剂时的反应速率提高了1 565倍。
冯潇 , 郭军 , 张丹 . （C5H7N2O2）4（SiMo12O40）的合成、结构及催化氧化碘离子研究[J]. 无机盐工业, 2021 , 53(9) : 109 -113 . DOI: 10.19964/j.issn.1006-4990.2020-0554
A novel organic-inorganic hybrid polyoxometalate（C5H7N2O2）4（SiMo12O40）（short for SiMo-12） was synthesized by the conventional aqueous solution method.The compounds were characterized by infrared spectroscopy（IR）,thermogravimetric analysis（TG）,single crystal and powder X-ray diffraction（XRD） and elemental analysis.With hydrogen peroxide as oxidant,SiMo-12 was used to catalyze the oxidation of iodine ions.The effect of catalyst dosage,oxidant dosage,pH,temperature and other factors on the reaction rate were investigated.The results showed that the compound belonged to the triclinic crystal system,P-1 spatial group,cell parameters a=1.097 58（4） nm、b=1.144 88（4） nm、c=1.252 66（4） nm、α=64.665（1）°、β=64.804（1）°、γ=83.441（1）°、V=1.282 89（8） nm3、Z=1、R=0.034 0、wR2=0.079 9.The structure of the compounds was composed of four 1-imidazoleacetic acid and a classical Keggin[SiMo12O40]4- unit and the organic ligands and the polyoxo-metalate anion formed a one-dimensional chain along x axis through electrostatic interaction,proton transfer and hydrogen bonding.These chains were parallel to each other,forming a two-dimensional layers parallel to the xy plane,which were connected by hydrogen bonds to obtain a three-dimensional network structure.The catalyst exhibited excellent catalytic activity in the oxidation of iodide ion,and the reaction rate reached 2.641 6×10-5 mol/（L·s） at the condition of c（SiMo-12）=2.0×10-4 mol/L、c（H2O2）= 2.0×10-3 mol/L、pH=1.4、T=50 ℃,which was 1 565 times higher than that without catalyst.
Key words： polyoxometallate; crystal structure; iodine ion; catalytic
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