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一维和二维基于噻唑的铜(II)配位聚合物:合成及其在二氧化碳捕集中的应用

1D and 2D Thiazole-Based Copper(II) Coordination Polymers: Synthesis and Applications in Carbon Dioxide Capture.

作者信息

Rossin Andrea, Tuci Giulia, Giambastiani Giuliano, Peruzzini Maurizio

机构信息

Istituto di Chimica dei Composti Organometallici (ICCOM-CNR), Via Madonna del Piano 10, 50019, Sesto Fiorentino (Italy), Fax: (+39) 055-5225203.

出版信息

Chempluschem. 2014 Mar;79(3):406-412. doi: 10.1002/cplu.201300360. Epub 2014 Jan 21.

DOI:10.1002/cplu.201300360
PMID:31986609
Abstract

The reaction of different copper(II) salts with a class of thiazole-based ligands under solvothermal conditions produces three crystalline 1D/2D coordination polymers: [Cu(κ-N-thiazole) (SiF )] (1 (1D)), {Cu[μ-(κ-N:κ-COO)-L ] ⋅(H O)} (2 (2D); HL =2-aminothiazole-5-carboxylic acid), and {Cu[μ-(κ-N:κ-COO)-L ] ⋅1.5 (H O)} (3 (2D); HL =thiazole-5-carboxylic acid). All the materials have been characterized through common solid-state techniques: single-crystal (XRD) and (variable-temperature) powder X-ray diffraction (PXRD), infrared spectroscopy (IR), thermogravimetric analysis combined with mass spectrometry (TGA-MS), and BET surface area and pore-size distribution measurements. Polymer 3 shows a porous structure made of squared channels formed by the ordered stacking of the planar sheets along the a crystallographic axis (inner surface area equal to 15 m  g , as inferred from N adsorption at T=77 K on the pre-activated form), and it has been exploited for CO physisorption at ambient temperature (T=303 K) and pressure (p max.=920 torr). A remarkable CO uptake equal to 9.0 wt % was recorded under these mild conditions, thereby making the material promising for carbon dioxide capture in post-combustion flue gas, in which the key factor for a successful performance is the high chemical selectivity for CO over N .

摘要

在溶剂热条件下,不同的铜(II)盐与一类噻唑基配体反应生成了三种晶体一维/二维配位聚合物:[Cu(κ-N-噻唑)(SiF )](1(一维))、{Cu[μ-(κ-N:κ-COO)-L ] ⋅(H O)}(2(二维);HL = 2-氨基噻唑-5-羧酸)和{Cu[μ-(κ-N:κ-COO)-L ] ⋅1.5 (H O)}(3(二维);HL = 噻唑-5-羧酸)。所有材料均通过常见的固态技术进行了表征:单晶(XRD)和(变温)粉末X射线衍射(PXRD)、红外光谱(IR)、热重分析结合质谱(TGA-MS)以及BET表面积和孔径分布测量。聚合物3呈现出一种由方形通道构成的多孔结构,这些通道是由平面片沿晶轴a有序堆叠形成的(根据在77 K下对预活化形式进行N吸附推断,内表面积等于15 m  g ),并且已被用于在环境温度(T = 303 K)和压力(p max.= 920 托)下的CO物理吸附。在这些温和条件下记录到了高达9.0 wt %的显著CO吸收量,从而使该材料有望用于燃烧后烟道气中的二氧化碳捕集,其中成功实现该性能的关键因素是对CO相对于N的高化学选择性。

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