Biomimetic O 2 adsorption in an iron metal–organic framework for air separation
Abstract
Bio-inspired motifs for gas binding and small molecule activation can be used to design more selective adsorbents for gas separation applications. Here, we report an iron metal–organic framework, Fe-BTTri (Fe3[(Fe4Cl)3(BTTri)8]2·18CH3OH, H3BTTri = 1,3,5-tris(1H-1,2,3-triazol-5-yl)benzene), that binds O2 in a manner similar to hemoglobin and therefore results in highly selective O2 binding. As confirmed by gas adsorption studies and Mössbauer and infrared spectroscopy data, the exposed iron sites in the framework reversibly adsorb substantial amounts of O2 at low temperatures by converting between high-spin, square-pyramidal Fe(II) centers in the activated material to low-spin, octahedral Fe(III)–superoxide sites upon gas binding. This change in both oxidation state and spin state observed in Fe-BTTri leads to selective and readily reversible O2 binding, with the highest reported O2/N2 selectivity for any iron-based framework.
- Authors:
-
- Department of Chemistry, University of California, Berkeley, USA
- Department of Chemistry, University of California, Berkeley, USA, Department of Chemical Engineering
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1582680
- Alternate Identifier(s):
- OSTI ID: 1760220
- Grant/Contract Number:
- SC0019992; AC02-06CH11357; AC02-05CH11231
- Resource Type:
- Published Article
- Journal Name:
- Chemical Science
- Additional Journal Information:
- Journal Name: Chemical Science Journal Volume: 11 Journal Issue: 6; Journal ID: ISSN 2041-6520
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United Kingdom
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Reed, Douglas A., Xiao, Dianne J., Jiang, Henry Z. H., Chakarawet, Khetpakorn, Oktawiec, Julia, and Long, Jeffrey R. Biomimetic O 2 adsorption in an iron metal–organic framework for air separation. United Kingdom: N. p., 2020.
Web. doi:10.1039/C9SC06047B.
Reed, Douglas A., Xiao, Dianne J., Jiang, Henry Z. H., Chakarawet, Khetpakorn, Oktawiec, Julia, & Long, Jeffrey R. Biomimetic O 2 adsorption in an iron metal–organic framework for air separation. United Kingdom. https://doi.org/10.1039/C9SC06047B
Reed, Douglas A., Xiao, Dianne J., Jiang, Henry Z. H., Chakarawet, Khetpakorn, Oktawiec, Julia, and Long, Jeffrey R. Wed .
"Biomimetic O 2 adsorption in an iron metal–organic framework for air separation". United Kingdom. https://doi.org/10.1039/C9SC06047B.
@article{osti_1582680,
title = {Biomimetic O 2 adsorption in an iron metal–organic framework for air separation},
author = {Reed, Douglas A. and Xiao, Dianne J. and Jiang, Henry Z. H. and Chakarawet, Khetpakorn and Oktawiec, Julia and Long, Jeffrey R.},
abstractNote = {Bio-inspired motifs for gas binding and small molecule activation can be used to design more selective adsorbents for gas separation applications. Here, we report an iron metal–organic framework, Fe-BTTri (Fe3[(Fe4Cl)3(BTTri)8]2·18CH3OH, H3BTTri = 1,3,5-tris(1H-1,2,3-triazol-5-yl)benzene), that binds O2 in a manner similar to hemoglobin and therefore results in highly selective O2 binding. As confirmed by gas adsorption studies and Mössbauer and infrared spectroscopy data, the exposed iron sites in the framework reversibly adsorb substantial amounts of O2 at low temperatures by converting between high-spin, square-pyramidal Fe(II) centers in the activated material to low-spin, octahedral Fe(III)–superoxide sites upon gas binding. This change in both oxidation state and spin state observed in Fe-BTTri leads to selective and readily reversible O2 binding, with the highest reported O2/N2 selectivity for any iron-based framework.},
doi = {10.1039/C9SC06047B},
journal = {Chemical Science},
number = 6,
volume = 11,
place = {United Kingdom},
year = {2020},
month = {2}
}
https://doi.org/10.1039/C9SC06047B
Web of Science
Works referenced in this record:
The mechanism of the poisoning of ammonia synthesis catalysts by oxygenates O2, CO and H2O: an in situ method for active surface determination
journal, January 1994
- Waugh, K. C.; Butler, D.; Hayden, B. E.
- Catalysis Letters, Vol. 24, Issue 1-2
Scorpionate-Type Coordination in MFU-4 l Metal-Organic Frameworks: Small-Molecule Binding and Activation upon the Thermally Activated Formation of Open Metal Sites
journal, May 2014
- Denysenko, Dmytro; Grzywa, Maciej; Jelic, Jelena
- Angewandte Chemie International Edition, Vol. 53, Issue 23
A review of air separation technologies and their integration with energy conversion processes
journal, May 2001
- Smith, A. R.; Klosek, J.
- Fuel Processing Technology, Vol. 70, Issue 2
Reversible CO Scavenging via Adsorbate-Dependent Spin State Transitions in an Iron(II)–Triazolate Metal–Organic Framework
journal, April 2016
- Reed, Douglas A.; Xiao, Dianne J.; Gonzalez, Miguel I.
- Journal of the American Chemical Society, Vol. 138, Issue 17
Making and Breaking the Dioxygen O−O Bond: New Insights from Studies of Synthetic Copper Complexes
journal, June 1997
- Tolman, William B.
- Accounts of Chemical Research, Vol. 30, Issue 6
Metal-Organic Frameworks as Biomimetic Catalysts
journal, October 2013
- Gu, Zhi-Yuan; Park, Jihye; Raiff, Aaron
- ChemCatChem, Vol. 6, Issue 1
Highly-Selective and Reversible O2 Binding in Cr3(1,3,5-benzenetricarboxylate)2
journal, June 2010
- Murray, Leslie J.; Dinca, Mircea; Yano, Junko
- Journal of the American Chemical Society, Vol. 132, Issue 23, p. 7856-7857
Metal–organic framework materials as catalysts
journal, January 2009
- Lee, JeongYong; Farha, Omar K.; Roberts, John
- Chemical Society Reviews, Vol. 38, Issue 5, p. 1450-1459
Hybrid porous solids past, present, future
journal, January 2008
- Férey, Gérard
- Chem. Soc. Rev., Vol. 37, Issue 1, p. 191-214
Hydrogen storage and carbon dioxide capture in an iron-based sodalite-type metal–organic framework (Fe-BTT) discovered via high-throughput methods
journal, January 2010
- Sumida, Kenji; Horike, Satoshi; Kaye, Steven S.
- Chemical Science, Vol. 1, Issue 2, p. 184-191
Low Temperature Syntheses and Reactivity of Cu 2 O 2 Active-Site Models
journal, July 2015
- Citek, Cooper; Herres-Pawlis, Sonja; Stack, T. Daniel P.
- Accounts of Chemical Research, Vol. 48, Issue 8
Isolated Fe Sites in Metal Organic Frameworks Catalyze the Direct Conversion of Methane to Methanol
journal, May 2018
- Osadchii, Dmitrii Y.; Olivos-Suarez, Alma I.; Szécsényi, Ágnes
- ACS Catalysis, Vol. 8, Issue 6
Oxygen binding to iron porphyrins
journal, November 1975
- Collman, James P.; Brauman, John I.; Suslick, Kenneth S.
- Journal of the American Chemical Society, Vol. 97, Issue 24
Thermodynamics of oxygen binding in natural and synthetic dioxygen complexes
journal, April 1984
- Niederhoffer, Eric C.; Timmons, James H.; Martell, Arthur E.
- Chemical Reviews, Vol. 84, Issue 2
Mössbauer spectroscopy of hemoglobin model compounds: Evidence for conformational excitation
journal, December 1975
- Spartalian, K.; Lang, G.; Collman, James P.
- The Journal of Chemical Physics, Vol. 63, Issue 12
Selective Binding of O 2 over N 2 in a Redox–Active Metal–Organic Framework with Open Iron(II) Coordination Sites
journal, September 2011
- Bloch, Eric D.; Murray, Leslie J.; Queen, Wendy L.
- Journal of the American Chemical Society, Vol. 133, Issue 37
Pore Environment Effects on Catalytic Cyclohexane Oxidation in Expanded Fe 2 (dobdc) Analogues
journal, October 2016
- Xiao, Dianne J.; Oktawiec, Julia; Milner, Phillip J.
- Journal of the American Chemical Society, Vol. 138, Issue 43
A Five-Coordinate Heme Dioxygen Adduct Isolated within a Metal–Organic Framework
journal, November 2014
- Anderson, John S.; Gallagher, Audrey T.; Mason, Jarad A.
- Journal of the American Chemical Society, Vol. 136, Issue 47
Hydrogen Storage and Selective, Reversible O 2 Adsorption in a Metal-Organic Framework with Open Chromium(II) Sites
journal, June 2016
- Bloch, Eric D.; Queen, Wendy L.; Hudson, Matthew R.
- Angewandte Chemie International Edition, Vol. 55, Issue 30
Synthetic oxygen carriers related to biological systems
journal, April 1979
- Jones, Robert D.; Summerville, David A.; Basolo, Fred.
- Chemical Reviews, Vol. 79, Issue 2
1.25 Å Resolution Crystal Structures of Human Haemoglobin in the Oxy, Deoxy and Carbonmonoxy Forms
journal, July 2006
- Park, Sam-Yong; Yokoyama, Takeshi; Shibayama, Naoya
- Journal of Molecular Biology, Vol. 360, Issue 3
Cooperative insertion of CO2 in diamine-appended metal-organic frameworks
journal, March 2015
- McDonald, Thomas M.; Mason, Jarad A.; Kong, Xueqian
- Nature, Vol. 519, Issue 7543
Dioxygen binding at a four-coordinate cobaltous porphyrin site in a metal–organic framework: structural, EPR, and O 2 adsorption analysis
journal, January 2016
- Gallagher, Audrey T.; Kelty, Margaret L.; Park, Jesse G.
- Inorganic Chemistry Frontiers, Vol. 3, Issue 4
Selective gas adsorption and separation in metal–organic frameworks
journal, January 2009
- Li, Jian-Rong; Kuppler, Ryan J.; Zhou, Hong-Cai
- Chemical Society Reviews, Vol. 38, Issue 5, p. 1477-1504
A structurally-characterized peroxomanganese( iv ) porphyrin from reversible O 2 binding within a metal–organic framework
journal, January 2018
- Gallagher, Audrey T.; Lee, Jung Yoon; Kathiresan, Venkatesan
- Chemical Science, Vol. 9, Issue 6
Comprehensive study of carbon dioxide adsorption in the metal–organic frameworks M 2 (dobdc) (M = Mg, Mn, Fe, Co, Ni, Cu, Zn)
journal, January 2014
- Queen, Wendy L.; Hudson, Matthew R.; Bloch, Eric D.
- Chem. Sci., Vol. 5, Issue 12
Cooperativity in O2 binding to iron porphyrins.
journal, March 1978
- Collman, J. P.; Brauman, J. I.; Rose, E.
- Proceedings of the National Academy of Sciences, Vol. 75, Issue 3
Functional Porous Coordination Polymers
journal, April 2004
- Kitagawa, Susumu; Kitaura, Ryo; Noro, Shin-ichiro
- Angewandte Chemie International Edition, Vol. 43, Issue 18, p. 2334-2375
Mössbauer studies on O 2 and CO binding to the heme iron in myoglobin
journal, July 1981
- Maeda, Y.; Harami, T.; Morita, Y.
- The Journal of Chemical Physics, Vol. 75, Issue 1
Design and synthesis of an exceptionally stable and highly porous metal-organic framework
journal, November 1999
- Li, Hailian; Eddaoudi, Mohamed; M., O'Keeffe
- Nature, Vol. 402, Issue 6759, p. 276-279
A Structural Mimic of Carbonic Anhydrase in a Metal-Organic Framework
journal, December 2018
- Wright, Ashley M.; Wu, Zhenwei; Zhang, Guanghui
- Chem, Vol. 4, Issue 12
Bioinspired Metal–Organic Framework for Trace CO 2 Capture
journal, September 2018
- Bien, Caitlin E.; Chen, Kai K.; Chien, Szu-Chia
- Journal of the American Chemical Society, Vol. 140, Issue 40
Synthetic Models of the Deoxy and Oxy Forms of the Non-Heme Dioxygen-Binding Protein Hemerythrin
journal, October 1998
- Mizoguchi, Tadashi J.; Lippard, Stephen J.
- Journal of the American Chemical Society, Vol. 120, Issue 42
On the bonding of FeO2 in hemoglobin and related dioxygen complexes.
journal, May 1977
- Reed, C. A.; Cheung, S. K.
- Proceedings of the National Academy of Sciences, Vol. 74, Issue 5
Separation of Xylene Isomers through Multiple Metal Site Interactions in Metal–Organic Frameworks
journal, February 2018
- Gonzalez, Miguel I.; Kapelewski, Matthew T.; Bloch, Eric D.
- Journal of the American Chemical Society, Vol. 140, Issue 9
A spin transition mechanism for cooperative adsorption in metal–organic frameworks
journal, September 2017
- Reed, Douglas A.; Keitz, Benjamin K.; Oktawiec, Julia
- Nature, Vol. 550, Issue 7674
Selective, Tunable O 2 Binding in Cobalt(II)–Triazolate/Pyrazolate Metal–Organic Frameworks
journal, May 2016
- Xiao, Dianne J.; Gonzalez, Miguel I.; Darago, Lucy E.
- Journal of the American Chemical Society, Vol. 138, Issue 22
Elucidation of the mode of binding of oxygen to iron in oxyhemoglobin by infrared spectroscopy
journal, November 1973
- Barlow, C. H.; Maxwell, J. C.; Wallace, W. J.
- Biochemical and Biophysical Research Communications, Vol. 55, Issue 1
Works referencing / citing this record:
Self-adjusting binding pockets enhance H 2 and CH 4 adsorption in a uranium-based metal–organic framework
journal, January 2020
- Halter, Dominik P.; Klein, Ryan A.; Boreen, Michael A.
- Chemical Science
Structure and redox tuning of gas adsorption properties in calixarene-supported Fe( ii )-based porous cages
journal, January 2020
- Deegan, Meaghan M.; Ahmed, Tonia S.; Yap, Glenn P. A.
- Chemical Science, Vol. 11, Issue 20