Hydrothermal Synthesis, Structure Characterization, Catalytic Property of Four Inorganic-Organic Hybrid Phosphomolybdates
Hydrothermal Synthesis, Structure Characterization, Catalytic Property of Four Inorganic-Organic Hybrid Phosphomolybdates
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四种无机-有机杂化磷钼酸盐的水热合成、结构表征及催化性能
DOI：
10.1002/zaac.200801336
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发表时间：
2009-11
期刊：
影响因子：
--
通讯作者：
许岩
中科院分区：
文献类型：
--
作者：
许岩
以MoO 3、Co（CH 3COO）2·4 H2O、三乙烯四胺（TETA）和50%磷酸为原料，水热法合成了4种新的基于{Mo 6P 4}单元的无机-有机杂化聚氧乙烯酸酯化合物，并用IR、TG、ICP和单晶X射线衍射对其进行了表征。化合物1（H4 TETA）2[（CoIITREN）2CoIIMoV12P8O52（OH）10]·4H2O [TREN =三（2-氨基乙基）胺]，其在pH = 8.9下获得，表示{Mo 6P 4}单元负载的过渡金属络合物，其中CoII原子被来自TREN的四个氮原子和来自PO 4四面体的一个氧原子五配位，另一个CoII原子通过共享六个μ3-O原子将两个{Mo 6P 4}单元连接在一起形成二聚体。在pH = 6.4下获得的化合物2（H4 TETA）2（C6 H18 N3）2[CoIIMoV 12 P8 O 54（OH）8]·5 H2O [C6 H15 N3 = N-（2-氨基乙基）哌嗪]显示二聚体阴离子[CoIIMoV 12 P8 O 54（OH）8]14-、两个完全质子化的TETA和两个质子化的N-（2-氨基乙基）哌嗪。从较低pH条件（3为4.5，4为3.1）获得的化合物3 [H4 TREN]4[CoIIMoV 12 P8 O 56（OH）6]·4 H2O和4 [H4 TETA]2[CoIIMoV 12 P8 O 48（OH）14]·4 H2O表现出与化合物2相同的二聚体阴离子，仅不同的阳离子。化合物1-4中的二聚阴离子与TETA（或其衍生物）通过氢键相互作用形成三维结构。客体水分子填充在孔道中，并与无机-有机杂化结构中的氧原子形成氢键，使结构更加稳定。并考察了这四种化合物在苯乙烯过氧化氢氧化反应中的催化性能。
Four new inorganic‐organic hybrid polyoxometalate compounds based on the {Mo6P4} unit have been hydrothermally synthesized from the reaction of MoO3, Co(CH3COO)2·4H2O, triethylenetetramine (TETA) and 50 % phosphorus acid, and characterized by IR, TG, ICP and single‐crystal X‐ray diffraction. Compound 1 (H4TETA)2[(CoIITREN)2CoIIMoV12P8O52(OH)10]·4H2O [TREN = tris(2‐aminoethyl)amine], which is obtained at pH = 8.9, represents a {Mo6P4} unit supported transition metal complex, in which the CoII atom is pentacoordinate by four nitrogen atoms from TREN and one oxygen atom from PO4 tetrahedron, and the other CoII atom joins two {Mo6P4} units together to form a dimer by sharing six μ3‐O atoms. Compound 2 (H4TETA)2(C6H18N3)2[CoIIMoV12P8O54(OH)8]·5H2O [C6H15N3 = N‐(2‐aminoethyl)piperazine] obtained at pH = 6.4 shows a dimer anion [CoIIMoV12P8 O54(OH)8]14–, two fully protonated TETA and two protonated N‐(2‐Aminoethyl)piperazine. Compounds 3 [H4TREN]4[CoIIMoV12P8O56(OH)6]·4H2O and 4 [H4TETA]2[CoIIMoV12P8O48 (OH)14]·4H2O obtained from lower pH conditions (4.5 for 3 and 3.1 for 4) exhibit the same dimer anion as compound 2 only different cations. As the secondary building unit, the discrete dimer anions in compound 1–4 and the TETA (or its derivatives) construct 3D structures by hydrogen bonding interaction. The guest water molecules are filled in the channels, and also involved in the hydrogen bonding with oxygen atoms from inorganic‐organic hybrid framework, which makes the structures more stable. The catalytic properties of the four compounds are also tested in the styrene oxidation with H2O2.
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影响因子：
1.9
作者：
Q. Bo;Z. Sun;G. Sun;Z. Zhang;C. L. Chen;Y. X. Li
通讯作者：
Q. Bo;Z. Sun;G. Sun;Z. Zhang;C. L. Chen;Y. X. Li
DOI：
10.1039/b010227j
发表时间：
2001
期刊：
Journal of The Chemical Society-dalton Transactions
影响因子：
--
作者：
Yan Xu;Dunru Zhu;Zijian Guo;Yu Shi;Kou-Lin Zhang;X. You
通讯作者：
Yan Xu;Dunru Zhu;Zijian Guo;Yu Shi;Kou-Lin Zhang;X. You
影响因子：
4.6
作者：
E. Burkholder;V. Golub;C. O'connor;J. Zubieta
通讯作者：
E. Burkholder;V. Golub;C. O'connor;J. Zubieta
影响因子：
3.3
作者：
Yunshan Zhou;Lijuan Zhang;H. Fun;J. Zuo;I. A. Razak;S. Chantrapromma;X. You
通讯作者：
Yunshan Zhou;Lijuan Zhang;H. Fun;J. Zuo;I. A. Razak;S. Chantrapromma;X. You
影响因子：
4.9
作者：
Yan Xu;Ji-qing Xu;Kou-Lin Zhang;Yong Zhang;X. You
通讯作者：
Yan Xu;Ji-qing Xu;Kou-Lin Zhang;Yong Zhang;X. You