Multi-dimensional Crystal Structuring of Complex Metal Oxide Catalysts of Group V and VI Elements by Unit-Assembling
Multi-dimensional Crystal Structuring of Complex Metal Oxide Catalysts of Group V and VI Elements by Unit-Assembling
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V、VI族元素复合金属氧化物催化剂的单元组装多维晶体结构
DOI：
10.1007/s11244-018-1077-0
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发表时间：
2019
影响因子：
3.6
通讯作者：
Wataru Ueda
中科院分区：
文献类型：
--
作者：
Satoshi Ishikawa;Zhenxin Zhang;Toru Murayama;Norihito Hiyoshi;Masahiro Sadakane;Wataru Ueda
介绍了通过单元组装方法合成的四种新型V族和VI族元素多孔晶态复合金属氧化物及其晶体结构形成机理。以多金属氧酸盐(POMS)为构筑单元，组装成微孔复合金属氧化物。在水热条件下，以[Mo6O21]为五方单元的MoVo-POMS与{VO}连接基组装形成微孔正交形(NH4)4[Mo30V4O106]{VO}6氧化物和三角(NH4)3[Mo19.5V1.5O69]{VO}6氧化物。以铋离子为连接剂，在水热条件下组装ε-Keggin Mo-POMS，得到了直径分别为0.77 nm和0.34 nm的立方体(NH_4)_4[Mo9.4V_3.6O_(40)]{Bi}_2晶体。一维阴离子钨硒酸盐分子线构筑块[SeW6O21]2SeW6O27首先由六方钨硒酸盐−单元[SeW6O27]线性连接而成，然后与CoIIion连接形成晶态微孔材料(NH4)0.4[SeW6O21]{Co(OH)}1.3。[W4O16]构建块与{VO}连接体有序连接，形成微孔骨架(K1.5(NH4)0.2H0.3[W4O16]{VO}3)，孔径0.43 nm，完全开放，小分子可接近。这些新型多孔晶型复合金属氧化物对烷烃氧化、乙醛氧化、醇氧化、过氧化氢氧化、NH3-SCR等均表现出较高的催化性能。
Four new porous crystalline complex metal oxide families based on group V and VI elements, all of which are synthesized through unit-assembling, are introduced along with crystal structure formation mechanism. Polyoxometalates (POMs) are utilized as building units and assembled for constructing microporous complex metal oxides. Assembling of MoVO-POMs having pentagonal units of [Mo6O21] with {VO} linkers under hydrothermal conditions forms microporous orthorhombic (NH4)4[Mo30V4O106] {VO}6oxide and trigonal (NH4)3[Mo19.5V1.5O69] {VO}6oxide. Assembling of ε-Keggin Mo-POMs with bismuth ions as a linker under a hydrothermal condition produces a cubic (NH4)4[Mo9.4V3.6O40] {Bi}2crystal with cages and channels with the diameter sizes of 0.77 and 0.34 nm, respectively. One dimensional anionic tungstosellenate molecular wire building block, [SeW6O21]2−n, is first formed by linear connection of hexagonal tungstosellenate POM units [SeW6O27] and then linked with the CoIIion to form a crystalline microporous materials, (NH4)0.4[SeW6O21] {Co(OH)}1.3. [W4O16] building blocks are orderly connected with {VO} linkers to form a microporous framework (K1.5(NH4)0.2H0.3[W4O16]{VO}3) with a pore diameter of 0.43 nm which is fully opened and is accessible to small molecules. These new porous crystalline complex metal oxides showed high catalytic performance for alkane oxidation, aldehyde oxidation, alcohol oxidation, H2O2oxidation, NH3-SCR, and so on.