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}₆ oxide and trigonal (NH₄)₃[Mo_19.5V_1.5O₆₉] {VO}₆ oxide. Assembling of ε-Keggin Mo-POMs with bismuth ions as a linker under a hydrothermal condition produces a cubic (NH₄)₄[Mo_9.4V_3.6O₄₀] {Bi}₂ crystal 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 Co^II ion 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 (K_1.5(NH₄)_0.2H_0.3[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, H₂O₂ oxidation, NH₃-SCR, and so on.

介绍了四个新的基于V和VI族元素的多孔晶体复合金属氧化物族，它们都是通过单元组装合成的，并介绍了其晶体结构形成机理。多金属氧酸盐（POM）用作建筑单元，并组装用于构建微孔复合金属氧化物。在水热条件下，将具有[Mo ₆ O ₂₁ ]五边形单元和{VO}接头的MoVO-POM组装成微孔正交晶体（NH ₄）₄ [Mo ₃₀ V ₄ O ₁₀₆ ] {VO} ₆氧化物和三角形（NH ₄）₃ [Mo _19.5 V _1.5 O₆₉ ] {VO} ₆氧化物。在水热条件下以铋离子为连接基的ε-KegginMo-POM的组装产生立方（NH ₄）₄ [Mo _9.4 V _3.6 O ₄₀ ] {Bi} ₂晶体，其晶体和晶体的笼形和通道尺寸为0.77和分别为0.34 nm。一个维阴离子tungstosellenate分子导线建筑砌块，[缝₆ ø ₂₁ ] ^2- _Ñ，首先由六边形tungstosellenate POM单元的线性连接形成[缝₆ Ò ₂₇ ]，然后与联合联^II离子形成结晶微孔材料，（NH ₄）_0.4 [SeW ₆ O ₂₁ ] {Co（OH）} _1.3。[W ₄ O ₁₆ ]构件与{VO}接头有序连接，形成孔径为0.43 nm的微孔骨架（K _1.5（NH ₄）_0.2 H _0.3 [W ₄ O ₁₆ ] {VO} ₃），其中完全打开，小分子可进入。这些新型的多孔晶体复合金属氧化物对烷烃氧化，醛氧化，醇氧化，H ₂ O表现出较高的催化性能。₂氧化，NH ₃ -SCR等。