Keggin型钨氧酸盐配合物的合成、结构及其电催化氧化水放氧性质研究
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摘要
论文采用水热合成方法,利用1:11和1:12系列的Keggin型多金属钨氧酸盐阴离子作为建筑单元,获得了九种迄今未见报道的多金属氧酸盐基配合物。采用单晶X-射线分析、元素分析、IR、XRD、TG和CV等技术对配合物的结构和性质进行了表征,并对部分配合物的电催化水产氧的性质进行了初步研究。
1.以1:11系列的钨氧酸盐阴离子为建筑单元,合成了三种多金属氧酸盐基配合物。[Hpy]_2{[Co(4,4'–Hbpy)_2(H_2O)_2][SiCoW_(11)O_(39)] (1) [Hpy]_2{[Co(4,4'–Hbpy)_2(H_2O)_2][GeCoW_(11)O_(39)] (2) [H_2bpy]_3[SiMnW_(11)O_(39)]·2H_2O (3)配合物1和2互为同构异质体,是由一维Keggin阴离子链[SiCoW_(11)O_(39)]n6n-与配合物片段[Co(4,4'–Hbpy)_2(H_2O)_2]n4n+构成的二维层状结构,层与层之间通过4,4'–bpy配体的相互嵌入形成类似拉链的三维超分子结构;配合物3是由Mn(II)取代的Keggin型多金属钨氧酸盐通过共用端氧形成的一维Z字型链。而且,我们还对配合物1-CPE在0.5 M HAc-NaAc (pH 4.5)缓冲液+1 mM [Ru(bpy)3]~(2+)溶液中的电化学性质做了详细的研究。结果发现,配合物1对电催化水产氧有一定的催化作用。
2.以Keggin型钨氧酸盐阴离子[SiW_(12)O_(40)]4-为建筑单元,合成了两种2D格子配合物。[{Mn(2,2'–bipy)_2}2{SiW_(12)O_(40)}] (4) [{Co(2,2'–bipy)_2}2{SiW_(12)O_(40)}] (5)配合物4和5互为同构异质体,是由Keggin型钨氧酸盐阴离子[SiW_(12)O_(40)]4-与配合物片段[M(2,2'–bipy)_2]~(2+)(M=Mn/Co)桥连形成的菱形格子结构。
3.以Keggin型钨氧酸盐阴离子[SiW_(12)O_(40)]4-为建筑单元,与软金属Cu、Ag配合物片段连接,合成了四种配合物。{Cu(4,4'–bipy)3/2·H_2O}2{SiW_(12)O_(40)}·4H_2O (6) [{Ag4(4,4'–bipy)3(2,2'–bipy)_2}{SiW_(12)O_(40)}] (7) [{Ag(py)_2}4{SiW_(12)O_(40)}] (8) [{Ag(4,4'–bipy)}2(Hpy)_2{SiW_(12)O_(40)}] (9)配合物6和7是由Keggin型钨氧酸盐阴离子[SiW_(12)O_(40)]4-与Cu(Ag)–bipy配合物片段构成的一维Z字型链状结构;配合物8和9分别是由配合物片段[{Ag(py)_2}4]4+和[{Ag(4,4'–bipy)}2(Hpy)_2]4+与Keggin型钨氧酸盐阴离子构成的二维层状结构。
In this paper, using series of 1:11 and 1:12 Keggin-Heteropolytungstates anions as building units, we get successfully nine new kinds of unreported polyoxometalate-based organic-inorganic complexes under hydrothermal condition. These complexes are characterized by X-ray single crystal diffractions, elemental analyses, IR, XRD, TG and CV. Some of them are preliminary studied on electrocatalytic oxidation of H_2O to O2.
1. Using series of 1:11 Keggin anions as building units, three kinds of organic-inorganic complexes were synthesized. [Hpy]_2{[Co(4,4'–Hbpy)_2(H_2O)_2][SiCoW_(11)O_(39)] (1) [Hpy]_2{[Co(4,4'–Hbpy)_2(H_2O)_2][GeCoW_(11)O_(39)] (2) [H_2bpy]3[SiMnW_(11)O_(39)]·2H_2O (3) Complexes 1 and 2 are isomorphic. They exhibit a 2D layered structure constructed from polymeric [XCoW_(11)O_(39)]6- [X=Si(1); X=Ge(2)] chains and [Co(4,4'–Hbpy)_2(H_2O)_2]4+ subunits.
The 4,4'–bpy molecules of neighboring layers are inserted and overlapped each other, generating a 3D supramolecular structure. In complex 3, the Keggin anions are connected through a common oxygen atom to give a one-dimensional chain. 1-CPEs are active for the electrocatalytic oxidation of H_2O to O2 in 0.5 M sodium acetate buffer (pH 4.5) containing 1 mM [Ru(bpy)3]_2+ solution.
2. Using Keggin [SiW_(12)O_(40)]4- anions as building units, two new complexes of 2D network structure were synthesized. [{Mn(2,2'–bipy)_2}2{SiW_(12)O_(40)}] (4) [{Co(2,2'–bipy)_2}2{SiW_(12)O_(40)}] (5) Complexes 1 and 2 are isomorphic. They are constructed into a diamond-shaped grid network through bridgeding polyoxometalate cluster {SiW_(12)O_(40)} and {M(2,2'–bipy)_2} fragments.
3. Using Keggin [SiW_(12)O_(40)]4- anions as building units, four Cu(II) and Ag(I) complexes were synthesized. {Cu(4,4'–bipy)3/2·H_2O}2{SiW_(12)O_(40)}·4H_2O (6) [{Ag4(4,4'–bipy)3(2,2'–bipy)_2}{SiW_(12)O_(40)}] (7) [{Ag(py)_2}4{SiW_(12)O_(40)}] (8) [{Ag(4,4'–bipy)}2(Hpy)_2{SiW_(12)O_(40)}] (9)
Complexes 6 and 7consist of [SiW_(12)O_(40)]4- anions and Cu(Ag)–bipy complex units, forming a one-dimensional chain structure. Complexes 8 and 9 exhibit a 2D structure constructed from [SiW_(12)O_(40)]4- and [{Ag(py)_2}4]4+ subunits for 8, [{Ag(4,4'–bipy)}2(Hpy)_2]4+ subunits for 9.
1.以1:11系列的钨氧酸盐阴离子为建筑单元,合成了三种多金属氧酸盐基配合物。[Hpy]_2{[Co(4,4'–Hbpy)_2(H_2O)_2][SiCoW_(11)O_(39)] (1) [Hpy]_2{[Co(4,4'–Hbpy)_2(H_2O)_2][GeCoW_(11)O_(39)] (2) [H_2bpy]_3[SiMnW_(11)O_(39)]·2H_2O (3)配合物1和2互为同构异质体,是由一维Keggin阴离子链[SiCoW_(11)O_(39)]n6n-与配合物片段[Co(4,4'–Hbpy)_2(H_2O)_2]n4n+构成的二维层状结构,层与层之间通过4,4'–bpy配体的相互嵌入形成类似拉链的三维超分子结构;配合物3是由Mn(II)取代的Keggin型多金属钨氧酸盐通过共用端氧形成的一维Z字型链。而且,我们还对配合物1-CPE在0.5 M HAc-NaAc (pH 4.5)缓冲液+1 mM [Ru(bpy)3]~(2+)溶液中的电化学性质做了详细的研究。结果发现,配合物1对电催化水产氧有一定的催化作用。
2.以Keggin型钨氧酸盐阴离子[SiW_(12)O_(40)]4-为建筑单元,合成了两种2D格子配合物。[{Mn(2,2'–bipy)_2}2{SiW_(12)O_(40)}] (4) [{Co(2,2'–bipy)_2}2{SiW_(12)O_(40)}] (5)配合物4和5互为同构异质体,是由Keggin型钨氧酸盐阴离子[SiW_(12)O_(40)]4-与配合物片段[M(2,2'–bipy)_2]~(2+)(M=Mn/Co)桥连形成的菱形格子结构。
3.以Keggin型钨氧酸盐阴离子[SiW_(12)O_(40)]4-为建筑单元,与软金属Cu、Ag配合物片段连接,合成了四种配合物。{Cu(4,4'–bipy)3/2·H_2O}2{SiW_(12)O_(40)}·4H_2O (6) [{Ag4(4,4'–bipy)3(2,2'–bipy)_2}{SiW_(12)O_(40)}] (7) [{Ag(py)_2}4{SiW_(12)O_(40)}] (8) [{Ag(4,4'–bipy)}2(Hpy)_2{SiW_(12)O_(40)}] (9)配合物6和7是由Keggin型钨氧酸盐阴离子[SiW_(12)O_(40)]4-与Cu(Ag)–bipy配合物片段构成的一维Z字型链状结构;配合物8和9分别是由配合物片段[{Ag(py)_2}4]4+和[{Ag(4,4'–bipy)}2(Hpy)_2]4+与Keggin型钨氧酸盐阴离子构成的二维层状结构。
In this paper, using series of 1:11 and 1:12 Keggin-Heteropolytungstates anions as building units, we get successfully nine new kinds of unreported polyoxometalate-based organic-inorganic complexes under hydrothermal condition. These complexes are characterized by X-ray single crystal diffractions, elemental analyses, IR, XRD, TG and CV. Some of them are preliminary studied on electrocatalytic oxidation of H_2O to O2.
1. Using series of 1:11 Keggin anions as building units, three kinds of organic-inorganic complexes were synthesized. [Hpy]_2{[Co(4,4'–Hbpy)_2(H_2O)_2][SiCoW_(11)O_(39)] (1) [Hpy]_2{[Co(4,4'–Hbpy)_2(H_2O)_2][GeCoW_(11)O_(39)] (2) [H_2bpy]3[SiMnW_(11)O_(39)]·2H_2O (3) Complexes 1 and 2 are isomorphic. They exhibit a 2D layered structure constructed from polymeric [XCoW_(11)O_(39)]6- [X=Si(1); X=Ge(2)] chains and [Co(4,4'–Hbpy)_2(H_2O)_2]4+ subunits.
The 4,4'–bpy molecules of neighboring layers are inserted and overlapped each other, generating a 3D supramolecular structure. In complex 3, the Keggin anions are connected through a common oxygen atom to give a one-dimensional chain. 1-CPEs are active for the electrocatalytic oxidation of H_2O to O2 in 0.5 M sodium acetate buffer (pH 4.5) containing 1 mM [Ru(bpy)3]_2+ solution.
2. Using Keggin [SiW_(12)O_(40)]4- anions as building units, two new complexes of 2D network structure were synthesized. [{Mn(2,2'–bipy)_2}2{SiW_(12)O_(40)}] (4) [{Co(2,2'–bipy)_2}2{SiW_(12)O_(40)}] (5) Complexes 1 and 2 are isomorphic. They are constructed into a diamond-shaped grid network through bridgeding polyoxometalate cluster {SiW_(12)O_(40)} and {M(2,2'–bipy)_2} fragments.
3. Using Keggin [SiW_(12)O_(40)]4- anions as building units, four Cu(II) and Ag(I) complexes were synthesized. {Cu(4,4'–bipy)3/2·H_2O}2{SiW_(12)O_(40)}·4H_2O (6) [{Ag4(4,4'–bipy)3(2,2'–bipy)_2}{SiW_(12)O_(40)}] (7) [{Ag(py)_2}4{SiW_(12)O_(40)}] (8) [{Ag(4,4'–bipy)}2(Hpy)_2{SiW_(12)O_(40)}] (9)
Complexes 6 and 7consist of [SiW_(12)O_(40)]4- anions and Cu(Ag)–bipy complex units, forming a one-dimensional chain structure. Complexes 8 and 9 exhibit a 2D structure constructed from [SiW_(12)O_(40)]4- and [{Ag(py)_2}4]4+ subunits for 8, [{Ag(4,4'–bipy)}2(Hpy)_2]4+ subunits for 9.
引文
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