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Negative cooperativity upon hydrogen bond-stabilized O2 adsorption in a redox-active metal–organic framework

Author

Listed:
  • Julia Oktawiec

    (University of California)

  • Henry Z. H. Jiang

    (University of California)

  • Jenny G. Vitillo

    (University of Minnesota)

  • Douglas A. Reed

    (University of California)

  • Lucy E. Darago

    (University of California)

  • Benjamin A. Trump

    (Center for Neutron Research)

  • Varinia Bernales

    (University of Minnesota)

  • Harriet Li

    (Massachusetts Institute of Technology)

  • Kristen A. Colwell

    (University of California)

  • Hiroyasu Furukawa

    (University of California
    Lawrence Berkeley National Laboratory)

  • Craig M. Brown

    (Center for Neutron Research
    University of Delaware)

  • Laura Gagliardi

    (University of Minnesota)

  • Jeffrey R. Long

    (University of California
    University of California
    Lawrence Berkeley National Laboratory)

Abstract

The design of stable adsorbents capable of selectively capturing dioxygen with a high reversible capacity is a crucial goal in functional materials development. Drawing inspiration from biological O2 carriers, we demonstrate that coupling metal-based electron transfer with secondary coordination sphere effects in the metal–organic framework Co2(OH)2(bbta) (H2bbta = 1H,5H-benzo(1,2-d:4,5-d′)bistriazole) leads to strong and reversible adsorption of O2. In particular, moderate-strength hydrogen bonding stabilizes a cobalt(III)-superoxo species formed upon O2 adsorption. Notably, O2-binding in this material weakens as a function of loading, as a result of negative cooperativity arising from electronic effects within the extended framework lattice. This unprecedented behavior extends the tunable properties that can be used to design metal–organic frameworks for adsorption-based applications.

Suggested Citation

  • Julia Oktawiec & Henry Z. H. Jiang & Jenny G. Vitillo & Douglas A. Reed & Lucy E. Darago & Benjamin A. Trump & Varinia Bernales & Harriet Li & Kristen A. Colwell & Hiroyasu Furukawa & Craig M. Brown &, 2020. "Negative cooperativity upon hydrogen bond-stabilized O2 adsorption in a redox-active metal–organic framework," Nature Communications, Nature, vol. 11(1), pages 1-11, December.
    • Handle: RePEc:nat:natcom:v:11:y:2020:i:1:d:10.1038_s41467-020-16897-z
    DOI: 10.1038/s41467-020-16897-z
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