skip to main content

DOE PAGESDOE PAGES

This content will become publicly available on June 11, 2019

Title: Reversible adsorption of nitrogen dioxide within a robust porous metal–organic framework

Nitrogen dioxide (NO 2) is a major air pollutant causing significant environmental and health problems. We report reversible adsorption of NO 2 in a robust metal–organic framework. Under ambient conditions, MFM-300(Al) exhibits a reversible NO 2 isotherm uptake of 14.1 mmol g -1, and, more importantly, exceptional selective removal of low-concentration NO 2 (5,000 to <1 ppm) from gas mixtures. Complementary experiments reveal five types of supramolecular interaction that cooperatively bind both NO 2 and N 2O 4 molecules within MFM-300(Al). We find that the in situ equilibrium 2NO 2 ↔ N 2O 4 within the pores is pressure-independent, whereas ex situ this equilibrium is an exemplary pressure-dependent first-order process. The coexistence of helical monomer–dimer chains of NO 2 in MFM-300(Al) could provide a foundation for the fundamental understanding of the chemical properties of guest molecules within porous hosts. Lastly, this work may pave the way for the development of future capture and conversion technologies.
Authors:
 [1] ;  [1] ;  [1] ;  [2] ;  [3] ;  [3] ;  [4] ;  [1] ; ORCiD logo [1] ;  [5] ;  [6] ;  [7] ; ORCiD logo [3] ;  [8] ;  [1] ;  [1]
  1. Univ. of Manchester (United Kingdom). School of Chemistry
  2. Univ. of Nottingham (United Kingdom). School of Chemistry
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical and Engineering Materials Division (CEMD), Neutron Sciences Directorate
  4. Univ. of Manchester (United Kingdom). School of Chemistry; Novosibirsk State Univ. (Russian Federation). International Tomography Center SB RAS
  5. Peking Univ., Beijing (China). College of Chemistry and Molecular Engineering
  6. European Synchrotron Radiation Facility (ESRF), Grenoble (France)
  7. Univ. of Nottingham (United Kingdom). School of Chemistry; Univ. of Nottingham Ningbo China, Ningbo (China). Dept. of Chemical and Environmental Engineering
  8. Univ. of Newcastle upon Tyne, Newcastle upon Tyne (United Kingdom)
Publication Date:
Grant/Contract Number:
AC05-00OR22725
Type:
Accepted Manuscript
Journal Name:
Nature Materials
Additional Journal Information:
Journal Volume: 17; Journal Issue: 8; Journal ID: ISSN 1476-1122
Publisher:
Springer Nature - Nature Publishing Group
Research Org:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org:
USDOE Laboratory Directed Research and Development (LDRD) Program; Engineering and Physical Sciences Research Council (EPSRC); Univ. of Manchester; Univ. of Nottingham; Russian Ministry of Science and Education
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE
OSTI Identifier:
1474849

Han, Xue, Godfrey, Harry G. W., Briggs, Lydia, Davies, Andrew J., Cheng, Yongqiang, Daemen, Luke L., Sheveleva, Alena M., Tuna, Floriana, McInnes, Eric J. L., Sun, Junliang, Drathen, Christina, George, Michael W., Ramirez-Cuesta, Anibal J., Thomas, K. Mark, Yang, Sihai, and Schröder, Martin. Reversible adsorption of nitrogen dioxide within a robust porous metal–organic framework. United States: N. p., Web. doi:10.1038/s41563-018-0104-7.
Han, Xue, Godfrey, Harry G. W., Briggs, Lydia, Davies, Andrew J., Cheng, Yongqiang, Daemen, Luke L., Sheveleva, Alena M., Tuna, Floriana, McInnes, Eric J. L., Sun, Junliang, Drathen, Christina, George, Michael W., Ramirez-Cuesta, Anibal J., Thomas, K. Mark, Yang, Sihai, & Schröder, Martin. Reversible adsorption of nitrogen dioxide within a robust porous metal–organic framework. United States. doi:10.1038/s41563-018-0104-7.
Han, Xue, Godfrey, Harry G. W., Briggs, Lydia, Davies, Andrew J., Cheng, Yongqiang, Daemen, Luke L., Sheveleva, Alena M., Tuna, Floriana, McInnes, Eric J. L., Sun, Junliang, Drathen, Christina, George, Michael W., Ramirez-Cuesta, Anibal J., Thomas, K. Mark, Yang, Sihai, and Schröder, Martin. 2018. "Reversible adsorption of nitrogen dioxide within a robust porous metal–organic framework". United States. doi:10.1038/s41563-018-0104-7.
@article{osti_1474849,
title = {Reversible adsorption of nitrogen dioxide within a robust porous metal–organic framework},
author = {Han, Xue and Godfrey, Harry G. W. and Briggs, Lydia and Davies, Andrew J. and Cheng, Yongqiang and Daemen, Luke L. and Sheveleva, Alena M. and Tuna, Floriana and McInnes, Eric J. L. and Sun, Junliang and Drathen, Christina and George, Michael W. and Ramirez-Cuesta, Anibal J. and Thomas, K. Mark and Yang, Sihai and Schröder, Martin},
abstractNote = {Nitrogen dioxide (NO2) is a major air pollutant causing significant environmental and health problems. We report reversible adsorption of NO2 in a robust metal–organic framework. Under ambient conditions, MFM-300(Al) exhibits a reversible NO2 isotherm uptake of 14.1 mmol g-1, and, more importantly, exceptional selective removal of low-concentration NO2 (5,000 to <1 ppm) from gas mixtures. Complementary experiments reveal five types of supramolecular interaction that cooperatively bind both NO2 and N2O4 molecules within MFM-300(Al). We find that the in situ equilibrium 2NO2 ↔ N2O4 within the pores is pressure-independent, whereas ex situ this equilibrium is an exemplary pressure-dependent first-order process. The coexistence of helical monomer–dimer chains of NO2 in MFM-300(Al) could provide a foundation for the fundamental understanding of the chemical properties of guest molecules within porous hosts. Lastly, this work may pave the way for the development of future capture and conversion technologies.},
doi = {10.1038/s41563-018-0104-7},
journal = {Nature Materials},
number = 8,
volume = 17,
place = {United States},
year = {2018},
month = {6}
}

Works referenced in this record:

A profile refinement method for nuclear and magnetic structures
journal, June 1969

EasySpin, a comprehensive software package for spectral simulation and analysis in EPR
journal, January 2006