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

Sergey N. Maximoff () and Berend Smit
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Sergey N. Maximoff: College of Chemistry, University of California
Berend Smit: College of Chemistry, University of California

Nature Communications, 2014, vol. 5, issue 1, 1-9

Abstract: Abstract 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.

Date: 2014
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Persistent link: https://EconPapers.repec.org/RePEc:nat:natcom:v:5:y:2014:i:1:d:10.1038_ncomms5032

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DOI: 10.1038/ncomms5032

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