Coordination-Chemistry Control of Proton Conductivity in the Iconic Metal鈥揙rganic Framework Material HKUST-1

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• 作者：Nak Cheon Jeong ; Bappaditya Samanta ; Chang Yeon Lee ; Omar K. Farha ; Joseph T. Hupp
• 刊名：The Journal of the American Chemical Society
• 出版年：2012
• 出版时间：January 11, 2012
• 年：2012
• 卷：134
• 期：1
• 页码：51-54
• 全文大小：308K
• 年卷期：v.134,no.1(January 11, 2012)
• ISSN：1520-5126

文摘

HKUST-1, a metal鈥搊rganic framework (MOF) material containing Cu^II-paddlewheel-type nodes and 1,3,5-benzenetricarboxylate struts, features accessible Cu^II sites to which solvent or other desired molecules can be intentionally coordinated. As part of a broader investigation of ionic conductivity in MOFs, we unexpectedly observed substantial proton conductivity with the 鈥渁s synthesized鈥?version of this material following sorption of methanol. Although HKUST-1 is neutral, coordinated water molecules are rendered sufficiently acidic by Cu^II to contribute protons to pore-filling methanol molecules and thereby enhance the alternating-current conductivity. At ambient temperature, the chemical identities of the node-coordinated and pore-filling molecules can be independently varied, thus enabling the proton conductivity to be reversibly modulated. The proton conductivity of HKUST-1 was observed to increase by 75-fold, for example, when node-coordinated acetonitrile molecules were replaced by water molecules. In contrast, the conductivity became almost immeasurably small when methanol was replaced by hexane as the pore-filling solvent.