Cu-3-trz-PMo12的合成、结构及催化氧化碘离子性能
收稿日期: 2021-11-19
网络出版日期: 2022-08-11
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);贵州省教育厅青年科技人才成长项目(黔科合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发课题(WFKF2017-03)
Synthesis,structure and catalytic oxidation performance of iodine ion of Cu-3-trz-PMo12
Received date: 2021-11-19
Online published: 2022-08-11
采用水热法合成了一例新的多酸基有机-无机杂化物,通过X射线单晶衍射、傅里叶变换红外光谱(IR)、热分析测试(TG)、X射线衍射分析(XRD)、扫描电子显微镜(SEM)、元素分析对化合物进行了表征。X射线单晶衍射分析结果表明,化合物的结构式为(PMo12O40) [Cu6(C2H4N4)6](PMo12O40)?H2O(简称为Cu-3-trz-PMo12),属于三方晶系,R-3空间群,晶胞参数a=1.756 66(3) nm、b=1.756 66(3) nm、c=2.303 24(6) nm、α=β=90°、γ=120°、V=6.155 2(3) nm3、Z=3、R1=0.023 8、wR2=0.059 2。化合物是由6个3-氨基-1,2,4-三氮唑、6个Cu+、两个经典的Keggin型[PMo12O40]3-及一个间隙水分子组成的二聚体,两个这样的二聚体通过氢键交替相连形成次级单元,每个次级单元之间又通过氢键作用进而形成一个三维超分子结构。催化研究表明,该非均相催化剂在催化过氧化氢氧化碘离子中表现出较为优异的催化活性且具有较稳定的可重复性。
袁常梅 , 郭军 , 张丹 , 张太文 . Cu-3-trz-PMo12的合成、结构及催化氧化碘离子性能[J]. 无机盐工业, 2022 , 54(8) : 145 -150 . DOI: 10.19964/j.issn.1006-4990.2021-0703
A new inorganic?organic hybrid compound based on polyoxometalates was synthesized by hydrothermal method,and characterized by X-ray single crystal diffraction,fourier transform infrared spectroscopy(IR),thermal analysis test(TG),X-ray diffraction analysis(XRD),scanning electron microscopy(SEM),element analysis.The X-ray single crystal diffraction analysis result showed that the structural formula of the compound was(PMo12O40)[Cu6(C2H4N4)6] (PMo12O40)?H2O(short for Cu-3-trz-PMo12),which was belonged to trigonal crystal system and R-3 space group.The crystal cell parameters were a=1.756 66(3) nm,b=1.756 66(3) nm,c=2.303 24(6) nm,α=β=90°,γ=120°,V=6.155 2(3) nm3,Z=3,R1=0.023 8,wR2=0.059 2.The compound was a dimer composed of six 3-amino-1,2,4-triazoles,six copper ions,two classical Keggin type[PMo12O40]3- and one interstitial water molecule.The two dimers were alternately linked by hydrogen bonds to form secondary units,and each secondary unit was formed by hydrogen bonds to form a three?dimensional supramolecular structure.The results showed that the heterogeneous catalyst had good catalytic activity and stable repeatability in the process oxidation of iodide ion by hydrogen peroxide.
Key words: polyoxometalate; crystal structure; catalytic oxidation; iodine ion
| 1 | 宋锡高.中国碘素产业发展现状[J].无机盐工业,2014,46(3):9-12. |
| 1 | SONG Xigao.Present development situation of China′s iodine industry[J].Inorganic Chemicals Industry,2014,46(3):9-12. |
| 2 | 张红映,雷学联.中国碘资源和碘化工生产与消费[J].磷肥与复肥,2011,26(2):76-78. |
| 2 | ZHANG Hongying, LEI Xuelian.Production and consumption of iodine resources and iodine chemical industry in China[J].Phosphate & Compound Fertilizer,2011,26(2):76-78. |
| 3 | SCHREIBER M, VIVEKANANDHAN S, MOHANTY A K,et al.Iodine treatment of lignin-cellulose acetate electrospun fibers:Enhancement of green fiber carbonization[J].ACS Sustainable Chemistry & Engineering,2015,3(1):33-41. |
| 4 | MADHU S, EVANS H A, DOAN-NGUYEN V V T,et al.Inside back cover:Infinite polyiodide chains in the pyrroloperylene?iodine complex:Insights into the starch?iodine and perylene?iodine complexes[J].Angewandte Chemie International Edition,2016,55(28).Doi:10.1002/anie.201604535 . |
| 5 | ZHAO Qing, LU Yanying, ZHU Zhiqiang,et al.Rechargeable lithi? |
| 5 | um?iodine batteries with iodine/nanoporous carbon cathode[J].Nano Letters,2015,15(9):5982-5987. |
| 6 | ZHANG Yongna, Hongying Lü, WANG Lu,et al.The oxidation of benzothiophene using the keggin?type lacunary polytungstophosphate as catalysts in emulsion[J].Journal of Molecular Catalysis A:Chemical,2010,332(1/2):59-64. |
| 7 | REZVANI M A, OVEISI M, ASLI M A NIA.Phosphotungestovanadate immobilized on PVA as an efficient and reusable nano catalyst for oxidative desulphurization of gasoline[J].Journal of Molecular Catalysis A:Chemical,2015,410:121-132. |
| 8 | BAI Xueli, HUANG Xin, WEN Liang,et al.A new strategy for the selective oxidation of alcohols catalyzed by a polyoxometalate?based hybrid surfactant in biphasic systems[J].Chemical Communications(Cambridge,England),2019,55(25):3598-3601. |
| 9 | 邬红龙,李文飞,郭军,等.碘吸收液中碘离子催化氧化结晶研究[J].广州化工,2014,42(15):54-57. |
| 9 | WU Honglong, LI Wenfei, GUO Jun,et al.Study on catalytic oxidation and crystallization of iodine ion in absorption liquid[J].Gu? |
| 9 | angzhou Chemical Industry,2014,42(15):54-57. |
| 10 | 周维珍,郭军,李文飞,等.膨润土负载磷钼酸催化碘离子氧化反应的研究[J].无机盐工业,2017,49(10):62-66. |
| 10 | ZHOU Weizhen, GUO Jun, LI Wenfei,et al.Research on catalytic oxidation reaction of iodine ions by bentonite?phosphomo? |
| 10 | lybdic acid catalysts[J].Inorganic Chemicals Industry,2017,49(10):62-66. |
| 11 | ZHU Yunfeng, ZHU Mingyuan, KANG Lihua,et al.Phosphotungstic acid supported on mesoporous graphitic carbon nitride as catalyst for oxidative desulfurization of fuel[J].Industrial & Engineering Chemistry Research,2015,54(7):2040-2047. |
| 12 | LIU Lingling, GUO Fangyuan, XU Jian,et al.Adsorption?enhanced oxidative desulfurization by a task?specific pyridinium?based porous ionic polymer[J].Fuel,2019,244:439-446. |
| 13 | REZVANI M A, MIRI O F.Synthesis and characterization of PWMn/NiO/PAN nanosphere composite with superior catalytic activity for oxidative desulfurization of real fuel[J].Chemical Engineering Journal,2019,369:775-783. |
| 14 | LI Na, MU Bao, LV Lei,et al.Assembly of new polyoxometalate-templated metal?organic frameworks based on flexible ligands[J].Journal of Solid State Chemistry,2015,226:88-93. |
| 15 | 赵婕,郭晴晴,郑玉国,等.2,6-二甲基-3,5-二(吡唑-3-基)吡啶/铜构筑的一维链状Keggin型杂多酸盐的合成、结构及电化学性质研究[J].人工晶体学报,2020,49(3):500-504,510. |
| 15 | ZHAO Jie, GUO Qingqing, ZHENG Yuguo,et al.Synthesis,structure and electrochemical properties of a 1D chain?like keggin?based hybrid constructed by 2,6-dimethyl-3,5-bis(pyrazole-3-yl) pyridine and copper[J].Journal of Synthetic Crystals,2020,49(3):500-504,510. |
| 16 | LIU Dongsheng, CHEN Wentong, YE Guangming,et al.Synthesis and characterization of an inorganic-organic hybrid copper coordination polymer based on well?defined Keggin polyanions[J].Inorganica Chimica Acta,2018,477:84-88. |
| 17 | SHA Jingquan, PENG Jun, TIAN Aixiang,et al.Assembly of multitrack Cu-N coordination polymeric chain?modified polyoxome? |
| 17 | talates influenced by polyoxoanion cluster and ligand[J].Crystal Growth & Design,2007,7(12):2535-2541. |
| 18 | SHA Jingquan, PENG Jun, LIU Hongsheng,et al.Asymmetrical polar modification of a bivanadium-capped Keggin POM by multiple Cu-N coordination polymeric chains[J].Inorganic Chemistry,2007,46(26):11183-11189. |
| 19 | BROWN I D, ALTERMATT D.Bond-valence parameters obtained from a systematic analysis of the Inorganic Crystal Structure Database[J].Acta Crystallographica Section B Structural Science,1985,41(4):244-247. |
| 19 | 上接第 124 页) |
| 19 | TANG Mengqi, LI Xiangrong, LIU Guowen,et al.Determination of free α-SiO2 content in mill scale by X-ray diffraction K value method[J].Rock and Mineral Analysis,2015,34(5):565-569. |
| 20 | 刘子铭,熊锐,关博文,等.不同pH值条件下水泥砂浆硫酸盐侵蚀损伤评价[J].硅酸盐通报,2016,35(7):2247-2253. |
| 20 | LIU Ziming, XIONG Rui, GUAN Bowen,et al.Damage evaluation of sulfate erosion to cement mortar under different pH-value conditions[J].Bulletin of the Chinese Ceramic Society,2016,35(7):2247-2253. |
| 21 | 李涛,朱鹏涛,张彬,等.硫酸盐侵蚀下混凝土内腐蚀反应-扩散过程的实验研究[J].硅酸盐通报,2020,39(1):50-55. |
| 21 | LI Tao, ZHU Pengtao, ZHANG Bin,et al.Experimental study on corrosion reaction?diffusion process of concrete under sulfate attack[J].Bulletin of the Chinese Ceramic Society,2020,39(1):50-55. |
| 22 | 高小建,马保国,邓红卫.胶凝材料组成对混凝土TSA硫酸盐侵蚀的影响[J].哈尔滨工业大学学报,2007,39(10):1554-1558. |
| 22 | GAO Xiaojian, MA Baoguo, DENG Hongwei.Influence of binder composition on the thaumasite form of sulfate attack of concre? |
| 22 | te[J].Journal of Harbin Institute of Technology,2007,39(10):1554-1558. |
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