Negative cooperativity upon hydrogen bond-stabilized O2 adsorption in a redox-active metal–organic framework
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 O 2 carriers, we demonstrate that coupling metal-based electron transfer with secondary coordination sp...
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Published in | Nature communications Vol. 11; no. 1; p. 3087 |
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Main Authors | , , , , , , , , , , , , |
Format | Journal Article |
Language | English |
Published |
London
Nature Publishing Group UK
18.06.2020
Nature Publishing Group Nature Portfolio |
Subjects | |
Online Access | Get full text |
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Summary: | 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 O
2
carriers, we demonstrate that coupling metal-based electron transfer with secondary coordination sphere effects in the metal–organic framework Co
2
(OH)
2
(bbta) (H
2
bbta = 1
H
,5
H
-benzo(1,2-
d:
4,5-
d
′)bistriazole) leads to strong and reversible adsorption of O
2
. In particular, moderate-strength hydrogen bonding stabilizes a cobalt(III)-superoxo species formed upon O
2
adsorption. Notably, O
2
-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.
Oxygen capture is attractive for catalysis, sensing, and separations, but engineering stable and selective adsorbents is challenging. Here the authors combine metal-based electron transfer with secondary coordination sphere effects in a metal-organic framework, leading to strong and reversible O
2
adsorption that also exhibits negative cooperativity. |
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Bibliography: | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 SC0019992; FG02−12ER16362; AC02-05CH11231 USDOE Office of Science (SC), Basic Energy Sciences (BES) |
ISSN: | 2041-1723 2041-1723 |
DOI: | 10.1038/s41467-020-16897-z |