A Metal鈥揙rganic Framework-Based Material for Electrochemical Sensing of Carbon Dioxide

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• 作者：Jeremiah J. Gassensmith ; Jeung Yoon Kim ; James M. Holcroft ; Omar K. Farha ; J. Fraser Stoddart ; Joseph T. Hupp ; Nak Cheon Jeong
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：June 11, 2014
• 年：2014
• 卷：136
• 期：23
• 页码：8277-8282
• 全文大小：454K
• 年卷期：v.136,no.23(June 11, 2014)
• ISSN：1520-5126

文摘

The free primary hydroxyl groups in the metal鈥搊rganic framework of CDMOF-2, an extended cubic structure containing units of six 纬-cyclodextrin tori linked together in cube-like fashion by rubidium ions, has been shown to react with gaseous CO₂ to form alkyl carbonate functions. The dynamic covalent carbon鈥搊xygen bond, associated with this chemisorption process, releases CO₂ at low activation energies. As a result of this dynamic covalent chemistry going on inside a metal鈥搊rganic framework, CO₂ can be detected selectively in the atmosphere by electrochemical impedance spectroscopy. The 鈥渁s-synthesized鈥?CDMOF-2 which exhibits high proton conductivity in pore-filling methanolic media, displays a 550-fold decrease in its ionic conductivity on binding CO₂. This fundamental property has been exploited to create a sensor capable of measuring CO₂ concentrations quantitatively even in the presence of ambient oxygen.