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

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

Research output: Contribution to journal › Article › peer-review

40 Scopus citations

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.

Original language	English (US)
Article number	3087
Journal	Nature communications
Volume	11
Issue number	1
DOIs	https://doi.org/10.1038/s41467-020-16897-z
State	Published - Jun 18 2020

Bibliographical note

Funding Information:
Experimental work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award DE-SC0019992, while computational efforts were supported by the Nanoporous Materials Genome Center, which is funded by the U.S. DoE, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences under award DE-FG02−17ER16362. X-ray powder diffraction data were collected on Beamline 17-BM-B at the Advanced Photon Source, a U.S. DoE Office of Science User Facility operated by Argonne National Laboratory. Use of the Advanced Photon Source at Argonne National Laboratory was supported by the U.S. DoE, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. Additionally, X-ray powder diffraction data was collected at Beamline 12.2.2 at the Advanced Light Source (ALS), which is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the U. S. DoE under Contract No. DE-AC02-05CH11231. Computational resources were provided in part by the Minnesota Supercomputing Institute (MSI) at the University of Minnesota. We are grateful to the National Science Foundation for graduate research fellowship support of J.O., D.A.R., and L.E.D. We further thank Prof. Peidong Yang for use of a scanning electron microscope; Dr. Matthew Koc, Dr. Benjamin Snyder, Dr. Tianpin Wu, Dr. Andrey Yakovenko, Dr. Wenqian Xu, Dr. Jacob Tarver, and Maria Paley for experimental assistance; Dr. Rebecca L. Siegelman, Dr. Miguel I. Gonzalez, Dr. Jeffrey D. Martell, Ari B. Turkiewicz, and Dr. Andy I. Nguyen for helpful discussions; and Dr. Katie R. Meihaus for editorial assistance.

Publisher Copyright:
© 2020, The Author(s).

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10.1038/s41467-020-16897-z

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Oktawiec, J., Jiang, H. Z. H., Vitillo, J. G., Reed, D. A., Darago, L. E., Trump, B. A., Bernales, V., Li, H., Colwell, K. A., Furukawa, H., Brown, C. M., Gagliardi, L., & Long, J. R. (2020). Negative cooperativity upon hydrogen bond-stabilized O₂ adsorption in a redox-active metal–organic framework. Nature communications, 11(1), Article 3087. https://doi.org/10.1038/s41467-020-16897-z

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

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.",

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

note = "Funding Information: Experimental work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award DE-SC0019992, while computational efforts were supported by the Nanoporous Materials Genome Center, which is funded by the U.S. DoE, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences under award DE-FG02−17ER16362. X-ray powder diffraction data were collected on Beamline 17-BM-B at the Advanced Photon Source, a U.S. DoE Office of Science User Facility operated by Argonne National Laboratory. Use of the Advanced Photon Source at Argonne National Laboratory was supported by the U.S. DoE, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. Additionally, X-ray powder diffraction data was collected at Beamline 12.2.2 at the Advanced Light Source (ALS), which is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the U. S. DoE under Contract No. DE-AC02-05CH11231. Computational resources were provided in part by the Minnesota Supercomputing Institute (MSI) at the University of Minnesota. We are grateful to the National Science Foundation for graduate research fellowship support of J.O., D.A.R., and L.E.D. We further thank Prof. Peidong Yang for use of a scanning electron microscope; Dr. Matthew Koc, Dr. Benjamin Snyder, Dr. Tianpin Wu, Dr. Andrey Yakovenko, Dr. Wenqian Xu, Dr. Jacob Tarver, and Maria Paley for experimental assistance; Dr. Rebecca L. Siegelman, Dr. Miguel I. Gonzalez, Dr. Jeffrey D. Martell, Ari B. Turkiewicz, and Dr. Andy I. Nguyen for helpful discussions; and Dr. Katie R. Meihaus for editorial assistance. Publisher Copyright: {\textcopyright} 2020, The Author(s).",

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T1 - Negative cooperativity upon hydrogen bond-stabilized O2 adsorption in a redox-active metal–organic framework

AU - Oktawiec, Julia

AU - Jiang, Henry Z.H.

AU - Vitillo, Jenny G.

AU - Reed, Douglas A.

AU - Darago, Lucy E.

AU - Trump, Benjamin A.

AU - Bernales, Varinia

AU - Li, Harriet

AU - Colwell, Kristen A.

AU - Furukawa, Hiroyasu

AU - Brown, Craig M.

AU - Gagliardi, Laura

AU - Long, Jeffrey R.

N1 - Funding Information: Experimental work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award DE-SC0019992, while computational efforts were supported by the Nanoporous Materials Genome Center, which is funded by the U.S. DoE, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences under award DE-FG02−17ER16362. X-ray powder diffraction data were collected on Beamline 17-BM-B at the Advanced Photon Source, a U.S. DoE Office of Science User Facility operated by Argonne National Laboratory. Use of the Advanced Photon Source at Argonne National Laboratory was supported by the U.S. DoE, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. Additionally, X-ray powder diffraction data was collected at Beamline 12.2.2 at the Advanced Light Source (ALS), which is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the U. S. DoE under Contract No. DE-AC02-05CH11231. Computational resources were provided in part by the Minnesota Supercomputing Institute (MSI) at the University of Minnesota. We are grateful to the National Science Foundation for graduate research fellowship support of J.O., D.A.R., and L.E.D. We further thank Prof. Peidong Yang for use of a scanning electron microscope; Dr. Matthew Koc, Dr. Benjamin Snyder, Dr. Tianpin Wu, Dr. Andrey Yakovenko, Dr. Wenqian Xu, Dr. Jacob Tarver, and Maria Paley for experimental assistance; Dr. Rebecca L. Siegelman, Dr. Miguel I. Gonzalez, Dr. Jeffrey D. Martell, Ari B. Turkiewicz, and Dr. Andy I. Nguyen for helpful discussions; and Dr. Katie R. Meihaus for editorial assistance. Publisher Copyright: © 2020, The Author(s).

PY - 2020/6/18

Y1 - 2020/6/18

N2 - 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.

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