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

Published

June 18, 2020

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

Pub Type

Journals

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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 O₂ Adsorption in a Redox-Active Metal-Organic Framework, Nature Chemistry, [online], https://tsapps.nist.gov/publication/get_pdf.cfm?pub_id=929205 (Accessed April 26, 2024)