Superexchange Charge Transport in Loaded Metal Organic Frameworks

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• 作者：Tobias Neumann ; Jianxi Liu ; Tobias Wächter ; Pascal Friederich ; Franz Symalla ; Alexander Welle ; Veronica Mugnaini ; Velimir Meded ; Michael Zharnikov ; Christof Wöll ; Wolfgang Wenzel
• 刊名：ACS Nano
• 出版年：2016
• 出版时间：July 26, 2016
• 年：2016
• 卷：10
• 期：7
• 页码：7085-7093
• 全文大小：473K
• 年卷期：0
• ISSN：1936-086X

文摘

In the past, nanoporous metal–organic frameworks (MOFs) have been mostly studied for their huge potential with regard to gas storage and separation. More recently, the discovery that the electrical conductivity of a widely studied, highly insulating MOF, HKUST-1, improves dramatically when loaded with guest molecules has triggered a huge interest in the charge carrier transport properties of MOFs. The observed high conductivity, however, is difficult to reconcile with conventional transport mechanisms: neither simple hopping nor band transport models are consistent with the available experimental data. Here, we combine theoretical results and new experimental data to demonstrate that the observed conductivity can be explained by an extended hopping transport model including virtual hops through localized MOF states or molecular superexchange. Predictions of this model agree well with precise conductivity measurements, where experimental artifacts and the influence of defects are largely avoided by using well-defined samples and the Hg-drop junction approach.