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Title: Modulating supramolecular binding of carbon dioxide in a redox-active porous metal-organic framework

Authors:
; ; ORCiD logo; ; ORCiD logo; ; ; ; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1388092
DOE Contract Number:
SC0001015
Resource Type:
Journal Article
Resource Relation:
Journal Name: Nature Communications; Journal Volume: 8; Related Information: CGS partners with University of California, Berkeley; University of California, Davis; Lawrence Berkeley National Laboratory; University of Minnesota; National Energy Technology Laboratory; Texas A&M University
Country of Publication:
United States
Language:
English
Subject:
membrane, carbon capture, materials and chemistry by design, synthesis (novel materials), synthesis (self-assembly), synthesis (scalable processing)

Citation Formats

Lu, Zhenzhong, Godfrey, Harry G. W., da Silva, Ivan, Cheng, Yongqiang, Savage, Mathew, Tuna, Floriana, McInnes, Eric J. L., Teat, Simon J., Gagnon, Kevin J., Frogley, Mark D., Manuel, Pascal, Rudić, Svemir, Ramirez-Cuesta, Anibal J., Easun, Timothy L., Yang, Sihai, and Schröder, Martin. Modulating supramolecular binding of carbon dioxide in a redox-active porous metal-organic framework. United States: N. p., 2017. Web. doi:10.1038/ncomms14212.
Lu, Zhenzhong, Godfrey, Harry G. W., da Silva, Ivan, Cheng, Yongqiang, Savage, Mathew, Tuna, Floriana, McInnes, Eric J. L., Teat, Simon J., Gagnon, Kevin J., Frogley, Mark D., Manuel, Pascal, Rudić, Svemir, Ramirez-Cuesta, Anibal J., Easun, Timothy L., Yang, Sihai, & Schröder, Martin. Modulating supramolecular binding of carbon dioxide in a redox-active porous metal-organic framework. United States. doi:10.1038/ncomms14212.
Lu, Zhenzhong, Godfrey, Harry G. W., da Silva, Ivan, Cheng, Yongqiang, Savage, Mathew, Tuna, Floriana, McInnes, Eric J. L., Teat, Simon J., Gagnon, Kevin J., Frogley, Mark D., Manuel, Pascal, Rudić, Svemir, Ramirez-Cuesta, Anibal J., Easun, Timothy L., Yang, Sihai, and Schröder, Martin. Mon . "Modulating supramolecular binding of carbon dioxide in a redox-active porous metal-organic framework". United States. doi:10.1038/ncomms14212.
@article{osti_1388092,
title = {Modulating supramolecular binding of carbon dioxide in a redox-active porous metal-organic framework},
author = {Lu, Zhenzhong and Godfrey, Harry G. W. and da Silva, Ivan and Cheng, Yongqiang and Savage, Mathew and Tuna, Floriana and McInnes, Eric J. L. and Teat, Simon J. and Gagnon, Kevin J. and Frogley, Mark D. and Manuel, Pascal and Rudić, Svemir and Ramirez-Cuesta, Anibal J. and Easun, Timothy L. and Yang, Sihai and Schröder, Martin},
abstractNote = {},
doi = {10.1038/ncomms14212},
journal = {Nature Communications},
number = ,
volume = 8,
place = {United States},
year = {Mon Feb 13 00:00:00 EST 2017},
month = {Mon Feb 13 00:00:00 EST 2017}
}
  • Hydrogen bonds dominate many chemical and biological processes, and chemical modification enables control and modulation of host–guest systems. Here in this paper we report a targeted modification of hydrogen bonding and its effect on guest binding in redox-active materials. MFM-300(V III) {[V III 2(OH) 2(L)], LH 4=biphenyl-3,3',5,5'-tetracarboxylic acid} can be oxidized to isostructural MFM-300(V IV), [V IV 2O 2(L)], in which deprotonation of the bridging hydroxyl groups occurs. MFM-300(V III) shows the second highest CO 2 uptake capacity in metal-organic framework materials at 298 K and 1 bar (6.0 mmol g -1) and involves hydrogen bonding between the OH group of the host and the O-donor of CO 2, which binds in an end-on manner, OH∙∙∙ =1.863(1) Å. In contrast, CO 2-loaded MFM-300(V IV) shows CO 2 bound side-on to the oxy group and sandwiched between two phenyl groups involving a unique O COmore » $$_2$$···c.g.phenyl interaction [3.069(2), 3.146(3) Å]. Lastly, the macroscopic packing of CO 2 in the pores is directly influenced by these primary binding sites.« less
  • Hydrogen bonds dominate many chemical and biological processes, and chemical modification enables control and modulation of host-guest systems. Here we report a targeted modification of hydrogen bonding and its effect on guest binding in redox-active materials. MFM-300(V III ) {[V III 2 (OH) 2 (L)], LH 4 =biphenyl-3,3',5,5'-tetracarboxylic acid} can be oxidized to isostructural MFM-300(V IV ), [V IV 2 O 2 (L)], in which deprotonation of the bridging hydroxyl groups occurs. MFM-300(V III ) shows the second highest CO 2 uptake capacity in metal-organic framework materials at 298 K and 1 bar (6.0 mmol g -1 ) and involvesmore » hydrogen bonding between the OH group of the host and the O-donor of CO 2 , which binds in an end-on manner, =1.863(1) Å. In contrast, CO 2 -loaded MFM-300(V IV ) shows CO 2 bound side-on to the oxy group and sandwiched between two phenyl groups involving a unique O CO2 ···c.g. phenyl interaction [3.069(2), 3.146(3) Å]. The macroscopic packing of CO 2 in the pores is directly influenced by these primary binding sites.« less
  • Supramolecular interactions are fundamental to host–guest binding in many chemical and biological processes. Direct visualization of such supramolecular interactions within host–guest systems is extremely challenging, but crucial to understanding their function. Within this paper, we report a comprehensive study that combines neutron scattering, synchrotron X-ray and neutron diffraction, and computational modelling to define the detailed binding at a molecular level of acetylene, ethylene and ethane within the porous host NOTT-300. This study reveals simultaneous and cooperative hydrogen-bonding, π···π stacking interactions and intermolecular dipole interactions in the binding of acetylene and ethylene to give up to 12 individual weak supramolecular interactionsmore » aligned within the host to form an optimal geometry for the selective binding of hydrocarbons. In addition, we also report the cooperative binding of a mixture of acetylene and ethylene within the porous host, together with the corresponding breakthrough experiments and analysis of adsorption isotherms of gas mixtures.« less
  • Supramolecular interactions are fundamental to host-guest binding in many chemical and biological processes. Direct visualization of such supramolecular interactions within host-guest systems is extremely challenging, but crucial to understanding their function. We report a comprehensive study that combines neutron scattering, synchrotron X-ray and neutron diffraction, and computational modelling to define the detailed binding at a molecular level of acetylene, ethylene and ethane within the porous host NOTT-300. This study reveals simultaneous and cooperative hydrogen-bonding, pi center dot center dot center dot pi stacking interactions and intermolecular dipole interactions in the binding of acetylene and ethylene to give up to 12more » individual weak supramolecular interactions aligned within the host to form an optimal geometry for the selective binding of hydrocarbons. We also report the cooperative binding of a mixture of acetylene and ethylene within the porous host, together with the corresponding breakthrough experiments and analysis of adsorption isotherms of gas mixtures.« less
  • The air-free reaction between FeCl₂ and H₄dobdc (dobdc{sup 4–} = 2,5-dioxido-1,4-benzenedicarboxylate) in a mixture of N,N-dimethylformamide (DMF) and methanol affords Fe₂(dobdc)·4DMF, a metal–organic framework adopting the MOF-74 (or CPO-27) structure type. The desolvated form of this material displays a Brunauer–Emmett–Teller (BET) surface area of 1360 m²/g and features a hexagonal array of one-dimensional channels lined with coordinatively unsaturated Fe{sup II} centers. Gas adsorption isotherms at 298 K indicate that Fe₂(dobdc) binds O₂ preferentially over N₂, with an irreversible capacity of 9.3 wt %, corresponding to the adsorption of one O₂ molecule per two iron centers. Remarkably, at 211 K, O₂more » uptake is fully reversible and the capacity increases to 18.2 wt %, corresponding to the adsorption of one O₂ molecule per iron center. Mössbauer and infrared spectra are consistent with partial charge transfer from iron(II) to O₂ at low temperature and complete charge transfer to form iron(III) and O₂{sup 2–} at room temperature. The results of Rietveld analyses of powder neutron diffraction data (4 K) confirm this interpretation, revealing O₂ bound to iron in a symmetric side-on mode with d{sub O–O} = 1.25(1) Å at low temperature and in a slipped side-on mode with dO–O = 1.6(1) Å when oxidized at room temperature. Application of ideal adsorbed solution theory in simulating breakthrough curves shows Fe₂(dobdc) to be a promising material for the separation of O₂ from air at temperatures well above those currently employed in industrial settings.« less