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

Xue Han; Harry G.W. Godfrey; Lydia Briggs; Andrew J. Davies; Yongqiang Cheng; Luke L. Daemen; Alena M. Sheveleva; Floriana Tuna; Eric J.L. McInnes; Junliang Sun; Christina Drathen; Michael W. George; Anibal J. Ramirez-Cuesta; K. Mark Thomas; Sihai Yang; Martin Schröder

doi:10.1038/s41563-018-0104-7

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

Xue Han, Harry G.W. Godfrey, Lydia Briggs, Andrew J. Davies, Yongqiang Cheng, Luke L. Daemen, Alena M. Sheveleva, Floriana Tuna, Eric J.L. McInnes, Junliang Sun, Christina Drathen, Michael W. George, Anibal J. Ramirez-Cuesta, K. Mark Thomas, Sihai Yang, Martin Schröder

Research output: Contribution to journal › Letter › peer-review

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Abstract

Nitrogen dioxide (NO₂) is a major air pollutant causing significant environmental^1,2 and health problems^3,4. 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. This work may pave the way for the development of future capture and conversion technologies.

Original language	English
Pages (from-to)	691-696
Number of pages	6
Journal	Nature Materials
Volume	17
Issue number	8
DOIs	https://doi.org/10.1038/s41563-018-0104-7
State	Published - Aug 1 2018

Funding

We thank the EPSRC (EP/I011870), the ERC (AdG 226593) and the Universities of Manchester and Nottingham for funding. We thank the EPSRC for funding of the EPSRC National Service for EPR Spectroscopy at Manchester. We are especially grateful to ORNL and the ESRF for access to the Beamlines VISION and ID22, respectively. We thank C. Dejoie for help at Beamline ID22 at the ESRF. The computing resources were made available through the VirtuES and the ICE-MAN projects, funded by the Laboratory Directed Research and Development program at ORNL. A.M.S. thanks the Russian Science Foundation (grant no. 17-73-10320) and the Royal Society of Chemistry for funding. M.S. acknowledges the Russian Ministry of Science and Education for the award of a Russian Megagrant (14.Z50.31.0006).

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Han, X., Godfrey, H. G. W., Briggs, L., Davies, A. J., Cheng, Y., Daemen, L. L., Sheveleva, A. M., Tuna, F., McInnes, E. J. L., Sun, J., Drathen, C., George, M. W., Ramirez-Cuesta, A. J., Thomas, K. M., Yang, S., & Schröder, M. (2018). Reversible adsorption of nitrogen dioxide within a robust porous metal–organic framework. Nature Materials, 17(8), 691-696. https://doi.org/10.1038/s41563-018-0104-7

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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 environmental1,2 and health problems3,4. 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. This work may pave the way for the development of future capture and conversion technologies.",

author = "Xue Han and Godfrey, {Harry G.W.} and Lydia Briggs and Davies, {Andrew J.} and Yongqiang Cheng and Daemen, {Luke L.} and Sheveleva, {Alena M.} and Floriana Tuna and McInnes, {Eric J.L.} and Junliang Sun and Christina Drathen and George, {Michael W.} and Ramirez-Cuesta, {Anibal J.} and Thomas, {K. Mark} and Sihai Yang and Martin Schr{\"o}der",

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doi = "10.1038/s41563-018-0104-7",

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Han, X, Godfrey, HGW, Briggs, L, Davies, AJ, Cheng, Y, Daemen, LL, Sheveleva, AM, Tuna, F, McInnes, EJL, Sun, J, Drathen, C, George, MW, Ramirez-Cuesta, AJ, Thomas, KM, Yang, S & Schröder, M 2018, 'Reversible adsorption of nitrogen dioxide within a robust porous metal–organic framework', Nature Materials, vol. 17, no. 8, pp. 691-696. https://doi.org/10.1038/s41563-018-0104-7

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T1 - Reversible adsorption of nitrogen dioxide within a robust porous metal–organic framework

AU - Han, Xue

AU - Godfrey, Harry G.W.

AU - Briggs, Lydia

AU - Davies, Andrew J.

AU - Cheng, Yongqiang

AU - Daemen, Luke L.

AU - Sheveleva, Alena M.

AU - Tuna, Floriana

AU - McInnes, Eric J.L.

AU - Sun, Junliang

AU - Drathen, Christina

AU - George, Michael W.

AU - Ramirez-Cuesta, Anibal J.

AU - Thomas, K. Mark

AU - Yang, Sihai

AU - Schröder, Martin

PY - 2018/8/1

Y1 - 2018/8/1

N2 - Nitrogen dioxide (NO2) is a major air pollutant causing significant environmental1,2 and health problems3,4. 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. This work may pave the way for the development of future capture and conversion technologies.

AB - Nitrogen dioxide (NO2) is a major air pollutant causing significant environmental1,2 and health problems3,4. 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. This work may pave the way for the development of future capture and conversion technologies.

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U2 - 10.1038/s41563-018-0104-7

DO - 10.1038/s41563-018-0104-7

M3 - Letter

C2 - 29891889

AN - SCOPUS:85048326971

SN - 1476-1122

VL - 17

SP - 691

EP - 696

JO - Nature Materials

JF - Nature Materials

IS - 8

ER -

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

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