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

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  • Sergey N. Maximoff

    (College of Chemistry, University of California)

  • Berend Smit

    (College of Chemistry, University of California
    Lawrence Berkeley National Laboratory)

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.

Suggested Citation

  • Sergey N. Maximoff & Berend Smit, 2014. "Redox chemistry and metal–insulator transitions intertwined in a nano-porous material," Nature Communications, Nature, vol. 5(1), pages 1-9, September.
  • Handle: RePEc:nat:natcom:v:5:y:2014:i:1:d:10.1038_ncomms5032
    DOI: 10.1038/ncomms5032
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