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

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; Laura Gagliardi; Jeffrey R Long

doi:10.1038/s41467-020-16897-z

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

Nat Commun. 2020 Jun 18;11(1):3087. doi: 10.1038/s41467-020-16897-z.

Authors

Julia Oktawiec¹, Henry Z H Jiang¹, Jenny G Vitillo², Douglas A Reed¹, Lucy E Darago¹, Benjamin A Trump³, Varinia Bernales², Harriet Li⁴, Kristen A Colwell⁵, Hiroyasu Furukawa^{1

6}, Craig M Brown^{3

7}, Laura Gagliardi², Jeffrey R Long^{8

9

10}

Affiliations

¹ Department of Chemistry, University of California, Berkeley, CA, 94720, USA.
² Department of Chemistry and Supercomputing Institute, University of Minnesota, Minneapolis, MN, 55455, USA.
³ National Institute of Standards and Technology, Center for Neutron Research, Gaithersburg, MD, 20899, USA.
⁴ Department of Aeronautics and Astronautics, Massachusetts Institute of Technology, Cambridge, MA, 02139, USA.
⁵ Department of Chemical and Biomolecular Engineering, University of California, Berkeley, CA, 94720, USA.
⁶ Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA.
⁷ Chemical and Biomolecular Engineering, University of Delaware, Newark, DE, 19716, USA.
⁸ Department of Chemistry, University of California, Berkeley, CA, 94720, USA. jrlong@berkeley.edu.
⁹ Department of Chemical and Biomolecular Engineering, University of California, Berkeley, CA, 94720, USA. jrlong@berkeley.edu.
¹⁰ Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA. jrlong@berkeley.edu.

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.

Publication types

Research Support, U.S. Gov't, Non-P.H.S.