skip to main content

DOE PAGESDOE PAGES

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

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 CO$$_2$$···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.
Authors:
 [1] ;  [1] ; ORCiD logo [2] ;  [3] ; ORCiD logo [1] ;  [1] ;  [1] ;  [4] ;  [4] ;  [5] ;  [2] ;  [2] ;  [3] ;  [6] ;  [1] ;  [1]
  1. Univ. of Manchester (United Kingdom). School of Chemistry
  2. Science and Technology Facilities Council (STFC), Oxford (United Kingdom). Rutherford Appleton Lab., ISIS Neutron Source
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical and Engineering Materials Division (CEMD)
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  5. Science and Technology Facilities Council (STFC), Harwell Campus, Oxford (United Kingdom). Diamond Light Source, Ltd.
  6. Cardiff Univ. (United Kingdom). School of Chemistry
Publication Date:
Grant/Contract Number:
AC05-00OR22725; AC02-05CH11231; SC0001015
Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 8; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Research Org:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org:
USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1356917
Alternate Identifier(s):
OSTI ID: 1379736

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., 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. 2017. "Modulating supramolecular binding of carbon dioxide in a redox-active porous metal-organic framework". United States. doi:10.1038/ncomms14212. https://www.osti.gov/servlets/purl/1356917.
@article{osti_1356917,
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 = {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(VIII) {[VIII2(OH)2(L)], LH4=biphenyl-3,3',5,5'-tetracarboxylic acid} can be oxidized to isostructural MFM-300(VIV), [VIV2O2(L)], in which deprotonation of the bridging hydroxyl groups occurs. MFM-300(VIII) shows the second highest CO2 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 CO2, which binds in an end-on manner, OH∙∙∙ =1.863(1) Å. In contrast, CO2-loaded MFM-300(VIV) shows CO2 bound side-on to the oxy group and sandwiched between two phenyl groups involving a unique OCO$_2$···c.g.phenyl interaction [3.069(2), 3.146(3) Å]. Lastly, the macroscopic packing of CO2 in the pores is directly influenced by these primary binding sites.},
doi = {10.1038/ncomms14212},
journal = {Nature Communications},
number = ,
volume = 8,
place = {United States},
year = {2017},
month = {2}
}

Works referenced in this record:

Carbon Dioxide Capture in Metal–Organic Frameworks
journal, September 2011
  • Sumida, Kenji; Rogow, David L.; Mason, Jarad A.
  • Chemical Reviews, Vol. 112, Issue 2, p. 724-781
  • DOI: 10.1021/cr2003272

Introduction to Metal–Organic Frameworks
journal, September 2011
  • Zhou, Hong-Cai; Long, Jeffrey R.; Yaghi, Omar M.
  • Chemical Reviews, Vol. 112, Issue 2, p. 673-674
  • DOI: 10.1021/cr300014x

Metal−Organic Frameworks with Exceptionally High Capacity for Storage of Carbon Dioxide at Room Temperature
journal, December 2005
  • Millward, Andrew R.; Yaghi, Omar M.
  • Journal of the American Chemical Society, Vol. 127, Issue 51, p. 17998-17999
  • DOI: 10.1021/ja0570032

Porous materials with optimal adsorption thermodynamics and kinetics for CO2 separation
journal, February 2013
  • Nugent, Patrick; Belmabkhout, Youssef; Burd, Stephen D.
  • Nature, Vol. 495, Issue 7439, p. 80-84
  • DOI: 10.1038/nature11893