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Negative Cooperativity upon Hydrogen Bond-Stabilized O2 Adsorption in a Redox-Active Metal-Organic Framework

Published

Author(s)

Julia Oktawiec, Henry Z. H. Jiang, Jenny G. Vitillo, Douglas A. Reed, Lucy E. Darago, Benjamin Trump, Varinia Bernales, Harriet Li, Kristen A. Colwell, Hiroyasu Furukawa, Craig Brown, Laura Gagliardi, Jeffrey R. Long

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.
Citation
Nature Chemistry
Volume
11
Issue
1

Keywords

Metal organic frameworks, Adsorption, negative cooperativity

Citation

Oktawiec, J. , Jiang, H. , Vitillo, J. , Reed, D. , Darago, L. , Trump, B. , Bernales, V. , Li, H. , Colwell, K. , Furukawa, H. , Brown, C. , Gagliardi, L. and Long, J. (2020), Negative Cooperativity upon Hydrogen Bond-Stabilized O<sub>2</sub> Adsorption in a Redox-Active Metal-Organic Framework, Nature Chemistry, [online], https://tsapps.nist.gov/publication/get_pdf.cfm?pub_id=929205 (Accessed June 24, 2024)

Issues

If you have any questions about this publication or are having problems accessing it, please contact reflib@nist.gov.

Created June 17, 2020, Updated October 12, 2021