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

Abstract

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.

Authors:
 [1];  [1];  [1];  [2];  [3];  [3];  [4];  [1]; ORCiD logo [1];  [5];  [6];  [7]; ORCiD logo [3];  [8];  [1];  [1]
+ Show Author Affiliations
  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:
Research Org.:
Oak Ridge National Laboratory (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
OSTI Identifier:
1474849
Grant/Contract Number:  
AC05-00OR22725
Resource 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
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

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., 2018. Web. doi:10.1038/s41563-018-0104-7.
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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. https://doi.org/10.1038/s41563-018-0104-7
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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. Mon . "Reversible adsorption of nitrogen dioxide within a robust porous metal–organic framework". United States. https://doi.org/10.1038/s41563-018-0104-7. https://www.osti.gov/servlets/purl/1474849.
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@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 = {Mon Jun 11 00:00:00 EDT 2018},
month = {Mon Jun 11 00:00:00 EDT 2018}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1038/s41563-018-0104-7
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Cited by: 113 works
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Figures / Tables:

Figure 1 Figure 1: NO2 adsorption, thermodynamics, selectivity and breakthrough data in MFM-300(Al). (a) Adsorption isotherms of NO2, SO2, CO2, CH4, N2, CO, H2, O2 and Ar in MFM-300(Al) at 298 K. (b) Variation of the thermodynamic parameters of isosteric heat of adsorption ($Q$$st$) and entropy ($ΔS$) for NO2 uptakes in MFM-300(Al).more » The isosteric heats of adsorption ($Q$$st$) of NO2 in MFM-300(Al) is ca. 50 kJ mol-1 at a surface coverage of 2-7 mmol g-1 and increases steadily to ca. 65 kJ mol-1 at higher surface coverage up to 10 mmol g-1. These $Q$$st$ values are higher than the heat of vaporization of N2O4 (38.1 kJ mol-1), consistent with the adsorption being driven by the enthalpy of adsorption and presence of specific host-guest binding interactions; the latter is entirely consistent with the diffraction and spectroscopic studies. Overall, $ΔS$ decreases slowly with increasing surface coverage, indicating the ordering of gases in the pore. (c) Comparison of IAST selectivities for equimolar mixtures of NO2/SO2 and NO2/CO2 (NO2/N2 data shown in SI) at 0.1-1.0 bar for MFM-300(Al) at 298 K. IAST calculations at low pressure (<0.1 bar) carries very large uncertainties due to the insufficient integration of spreading pressure and are thus not reported. (d) Dimensionless breakthrough curve of 0.5% NO2 (5000 ppm) diluted in He/N2 under both dry and wet conditions through a fixed-bed packed with MFM-300(Al) at 298 K and 1 bar. (e) Dimensionless breakthrough curve of 0.4% NO2 (4000 ppm) and 15% CO2 (v/v) diluted in He through a fixed-bed packed with MFM-300(Al) at 298 K and 1 bar. (f) Dimensionless breakthrough curve of 0.16% NO2 (1666 ppm) and 0.34% SO2 (3334 ppm) diluted through He in a fixed-bed packed with MFM-300(Al) at 298 K and 1 bar.« less
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