铜配合物修饰的Dawson型钨磷酸盐的合成、晶体结构和催化性能

doi:10.11944/j.issn.1000-0518.2015.04.140277

摘要/Abstract

摘要：

在水热条件下,Cu(Ⅱ)-H₂biim配合物与Dawson型钨磷酸盐构筑了1个无机-有机杂化化合物[Cu(H₂biim)₂(H₂O)][{Cu(H₂biim)₂}₂(P₂W₁₈O₆₂)]·11H₂O(1)(H₂biim=2,2'-联咪唑)。通过单晶X射线衍射、红外光谱(IR)、X射线粉末衍射(XRD)、元素分析、电化学分析等技术手段对其进行了表征。结构分析表明,在化合物1分子中,[P₂W₁₈O₆₂]^6-单元作为双齿配体与2个Cu²⁺离子配位形成双支撑的杂多阴离子[{Cu(H₂biim)₂}₂(P₂W₁₈O₆₂)]^2-,在其外部有1个游离的[Cu(H₂biim)₂(H₂O)]²⁺ 和11个H₂O分子。 H₂biim分子与杂多阴离子/H₂O分子间存在氢键,通过氢键、静电和π-π堆积作用,进一步构成具有3D结构的晶体材料。该晶体化合物对H₂O₂和NaNO₂的还原具有良好的电催化作用;同时,作为酸催化剂用于合成环己酮乙二醇缩酮反应,催化活性高,可重复使用。

关键词: 铜配合物, Dawson结构, 钨磷酸盐, 联咪唑, 电催化, 酸催化

Abstract:

An inorganic-organic hybrid compound [Cu(H₂biim)₂(H₂O)][{Cu(H₂biim)₂}₂(P₂W₁₈ O₆₂)]·11H₂O(H₂biim=2,2'-biimidazole)(1) has been hydrothermally constructed by the reaction of Cu(Ⅱ)-H₂biim complexes and Dawson-type tungstophosphate, and characterized by single-crystal X-ray diffraction, infrared spectroscopy(IR), X-ray powder diffraction(XRD), elemental analysis and electrochemical analysis. Structural analysis shows that the polyanion [P₂W₁₈O₆₂]^6-, as a bidentate ligand, coordinates with two Cu²⁺ ions to form a bi-Cu(Ⅱ)-supporting heteropolyanion [{Cu(H₂biim)₂}₂(P₂W₁₈O₆₂)]^2-, which is surrounded by an isolated [Cu(H₂biim)₂(H₂O)]²⁺ and eleven H₂O molecules. The presence of hydrogen bonds between H₂biim molecules and polyoxoanion or water molecules, in company with the synergistic effect of electrostatic interactions and π-π stack, leads to the formation of a crystal material with 3D framework further. Compound 1 displays good electrocatalytic activity toward the reduction of H₂O₂ and Na₂NO₂. Meanwhile it is also a good acid-catalyst for the synthesis of cyclohexanone ethylene ketal and can be recycled.

Key words: copper complex, dawson structure, tungstophosphate, biimidazole, electrocatalytic activity, catalytic activity

中图分类号:

O614.1

朱浩天, 李晓辉, 白建萍, 卢明达, 安悦, 由万胜. 铜配合物修饰的Dawson型钨磷酸盐的合成、晶体结构和催化性能[J]. 应用化学, 2015, 32(4): 433-441.

ZHU Haotian, LI Xiaohui, BAI Jianping, LU Mingda, AN Yue , YOU Wansheng . Synthesis, Crystal Structure and Catalytic Activity of a Dawson-type Tungstophosphate Decorated by Copper Complexes[J]. Chinese Journal of Applied Chemistry, 2015, 32(4): 433-441.

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