Redox chemistry and metal–insulator transitions intertwined in a nano-porous material

Metal-organic frameworks are nano-porous adsorbents of relevance to gas separation and catalysis, and separation of oxygen from air is essential to diverse industrial applications. The ferrous salt of 2,5-dihydroxy-terephthalic acid, a metal-organic framework of the MOF74 family, can selectively adsorb oxygen in a manner that defies the classical picture: adsorption sites either do or do not share electrons over a long range. Here we propose, and then justify phenomenologically and computationally, a mechanism. Charge-transfer-mediated adsorption of electron acceptor oxygen molecules in the metal-organic framework, which is a quasi-one-dimensional electron-donor semiconductor, drives and is driven by quasi-one-dimensional metal–insulator–metal transitions that localize or delocalize the quasi-one-dimensional electrons. This mechanism agrees with the empirical evidence, and predicts a class of nano-porous semiconductors or metals and potential adsorbents and catalysts in which chemistry and metal–insulator–metal transitions intertwine.


Published in:
Nature Communications, 5
Year:
2014
Publisher:
Nature Publishing Group, a division of Macmillan Publishers Limited. All Rights Reserved.
ISSN:
2041-1723
Note:
Supplementary information available for this article at http://www.nature.com/ncomms/2014/140606/ncomms5032/suppinfo/ncomms5032_S1.html
Laboratories:




 Record created 2014-08-14, last modified 2018-03-18

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Maximoff-2014-Redox chemistry and metal–insula - Download fulltextPDF
Maximoff-2014-Redox chemistry and metal–insul1 - Download fulltextPDF
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