一个铜掺杂的缺位Keggin型链状杂化材料的合成与表征
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摘要
对过渡金属掺杂的缺位Keggin型簇基杂化材料的合成方法及表征手段进行了研究。采用水热合成技术制备了一个具有新颖结构的无机-有机杂化材料{K(H2O)2[Cu0.5(en)][CuSiW11O39]}(H2en)2(1,en=乙二胺),利用元素分析、红外光谱、X射线光电子能谱、TG及X射线单晶衍射等技术对晶体结构进行了分析,并对化合物1的光催化性能进行了研究。结构分析显示,簇基杂化材料是由过渡金属掺杂的缺位Keggin型簇阴离子[SiCuW11O39]6-通过(μ-O)单桥氧原子连接成以簇阴离子为结构单元的1-D链,两个相邻的1-D簇阴离子链再经K(H2O)2[Cu0.5(en)]配合物阳离子通过共价键连接成新颖的1-D"梯子"状双链,质子化的乙二胺填充于网络之中。
In this paper,the crystal synthesis and performance of inorganic-organic hybrid materials with metallic oxygen cluster were studied. A new hybrid material {K(H2 O)2[Cu0.5(en)][CuSiW11 O39]}(H2 en)2(1,en=ethylenediamine)has been hydrothermally synthesized and characterized by elemental analysis,IR,XPS,TG and single-crystal X-ray diffraction analysis, and the photocatalytic property of 1 has been investigated. Compound 1 is possessed of 1 D chain-like structure {[CuSiW11 O39]6-}nwhich was built up Keggin type lacunary polyoxoanions with copper doped[CuSiW11 O39]6-,two neighbor 1-D chains are linked by {K(H2 O)2[Cu0.5(en)]}2 +cations to build a ladder-like chain structure,which is further interconnected into a 3-D supramolecular framework via hydrogen bonding interactions. Two protonated H2 en2+is located in the holes of the network.
In this paper,the crystal synthesis and performance of inorganic-organic hybrid materials with metallic oxygen cluster were studied. A new hybrid material {K(H2 O)2[Cu0.5(en)][CuSiW11 O39]}(H2 en)2(1,en=ethylenediamine)has been hydrothermally synthesized and characterized by elemental analysis,IR,XPS,TG and single-crystal X-ray diffraction analysis, and the photocatalytic property of 1 has been investigated. Compound 1 is possessed of 1 D chain-like structure {[CuSiW11 O39]6-}nwhich was built up Keggin type lacunary polyoxoanions with copper doped[CuSiW11 O39]6-,two neighbor 1-D chains are linked by {K(H2 O)2[Cu0.5(en)]}2 +cations to build a ladder-like chain structure,which is further interconnected into a 3-D supramolecular framework via hydrogen bonding interactions. Two protonated H2 en2+is located in the holes of the network.
引文
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[5]张学键,李春,古亮,等.掺镱钇铝石榴石激光晶体生长与性能研究[J].长春理工大学学报:自然科学版,2012,35(1):134-137.
[6]李沛航,崔梦楠,万玉春.h-BN掺杂对金刚石结构的影响[J].长春理工大学学报:自然科学版,2015,38(5):72-75.
[7] Han ZhangGang,Chang XiaoQing,Yan JinShuang,et al. An unusual metalic oxygen cluster of a{AlMo12O40(MoO2)}[J].Inorg. Chem.,2014,53(2):670-672.
[8] Xiao LiNa,Wang Yan,Chen Yan,et al,A Novel polyoxometalate tri-supported mixed-valent transition metal coordination complex[J].Inorg. Chem.Commun.,2010,13(10):1217-1220.
[9] Zhang QingBin,Lu YuKun,Liu YaBing,et al. Synthesis and characterization of the first polyoxometalate possessing bicapped by antimonyα-Keggin structure(C2N2H9)2[PMoV5MoVI7SbIII2O40]·4H2O[J].Inorg. Chem. Commun.,2006(9):544-547.
[10] Xu JiQing,Wang RenZhang,Yang GouYu,et al.Metal oxo cluster-supported transition metal oxides:hydrothermal synthesis and characterization of[{M(phen)2}2(Mo8O26)](M=Ni and Co)[J].Chem. Commun,1999,(11):983-984.
[11] Liu CaiMing,Zhang DeQing,Zhu DaoBen.Oneand two-dimensional coordination polymers constructed from bicapped Keggin mixed molybdenum-vanadium heteropolyoxoanions and polynuclear copper(I)clusters bridged by asymmetrical bipyridine(2,4’-bipy and 2,3’-bipy)ligands[J].Cryst. Growth Des,2006(6):524-529.
[12]刘红.三缺位Keggin型杂多钨酸盐与过渡金属的配位组装、晶体结构和磁性研究[D].长春:东北师范大学,2007:3-19.
[13]谭荣欣.以Keggin结构多金属氧酸盐为建筑单元的取代和夹心结构化合物的研究[D].长春:东北师范大学,2007:6-11.
[14] Gnsberg A.P,Inorganic Synthesis[M].New York:Wiley,1990.
[15] Sheldrick GM. Program for Empirical X-ray Absorption Correction[M].Bruker-Nonius,1990.
[16]吴春燕,刘希龙,沈国英,等.Keggin型铜取代磷钨杂多阴离子可见光催化降解罗丹明B[J].应用化学,2012,29(9):1030-1035.