一种双吡啶双酰胺配体修饰的Keggin型硅钼酸盐基配合物的合成、结构与催化性能

doi:10.11944/j.issn.1000-0518.2016.01.150199

摘要/Abstract

摘要：

水热反应条件下制备了一个基于半刚性双吡啶双酰胺配体3-bpcd(N,N'-双(3-吡啶)环己烷-1,4-双甲酰胺)和Keggin型多金属氧酸盐的银配合物{[Ag₂(3-bpcd)₃][Ag(3-bpcd)(SiMo₁₂O₄₀)]₂(3-H₂bpcd)₂}·7H₂O,并通过红外光谱、元素分析和X射线单晶衍射等技术手段确定了其晶体结构。结构分析表明该配合物属于三斜晶系,P-1空间群,晶胞参数a=1.3597(5) nm,b=1.4949(5) nm,c=2.5249(10) nm,α=88.998(6)°,β=88.856(7)°,γ=67.458(6)°,V=4.739(3) nm³,M_r=6471.02,D_c=2.261 g/cm³,Z=1,S=0.955,F(000)=3124,R₁=0.0768,wR₂=0.1936。配合物是由一维[Ag(3-bpcd)(SiMo₁₂O₄₀)]₂^6-链、双金属[Ag₂(3-bpcd)₃]²⁺结构单元、2个未配位的质子化有机配体3-H₂bpcd和7个结晶水共同组成的复杂结构,多种结构单元间通过氢键作用形成三维超分子网络结构。标题配合物修饰的碳糊电极对NO₂^-有好的电催化还原活性,此配合物作为催化剂对罗丹明B的降解有显著的催化效果。 CCDC:1401875

关键词: 多金属氧酸盐, 配合物, 晶体结构, 电催化性质, 光催化活性

Abstract:

A new Keggin-type polyoxometalate-based silver compound constructed from a semi-rigid bis-pyridyl-bis-amide ligand 3-bpcd(N,N'-bis(pyridin-3-yl)cyclohexane-1,4-dicarboxamide), {[Ag₂(3-bpcd)₃][Ag(3-bpcd)(SiMo₁₂O₄₀)]₂(3-H₂bpcd)₂}·7H₂O was prepared under the hydrothermal condition and characterized by IR, element analysis and X-ray single-crystal diffraction. The title complex is a triclinic system with space group P-1, whose cell parameters are a=1.3597(5) nm, b=1.4949(5) nm, c=2.5249(10) nm, α=88.998(6)°, β=88.856(7)°, γ=67.458(6)°, V=4.739(3) nm³, M_r=6471.02, D_c=2.261g/cm³, Z=1, S=0.955, F(000)=3124, R₁=0.0768, wR₂=0.1936. In this compound, a [Ag(3-bpcd)(SiMo₁₂O₄₀)]₂^6- one-dimensional chain, a dinuclear [Ag₂(3-bpcd)₃]²⁺ structure unit and two non-coordinated protonated organic ligands 3-bpcd coexists. These structural units are extended into the three-dimensional supramolecular network by the hydrogen bonding interactions. The title complex modified carbon paste electrode displays good electrocatalytic activity toward NO₂^- reduction. Additionally, this complex possesses a remarkable photocatalytic ability for the degradation of Rhodamine B(RhB) dye. CCDC:1401875.

Key words: polyoxometalate, compound, crystal structure, electrocatalytic property, photocatalytic activity

林宏艳, 曾凌, 王青林, 刘国成, 田原. 一种双吡啶双酰胺配体修饰的Keggin型硅钼酸盐基配合物的合成、结构与催化性能[J]. 应用化学, 2016, 33(1): 76-83.

LIN Hongyan, ZENG Ling, WANG Qinglin, LIU Guocheng, TIAN Yuan. Synthesis, Structure and Catalytic Properties of the Keggin-type Silicomolybdenate-based Silver Compound Modified by a Bis-pyridyl-bis-amide Ligand[J]. Chinese Journal of Applied Chemistry, 2016, 33(1): 76-83.

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