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Capture of nitrogen dioxide and conversion to nitric acid in a porous metal–organic framework


Air pollution by nitrogen oxides, NOx, is a major problem, and new capture and abatement technologies are urgently required. Here, we report a metal–organic framework (Manchester Framework Material 520 (MFM-520)) that can efficiently confine dimers of NO2, which results in a high adsorption capacity of 4.2 mmol g–1 (298 K, 0.01 bar) with full reversibility and no loss of capacity over 125 cycles. Treatment of NO2@MFM-520 with water in air leads to a quantitative conversion of the captured NO2 into HNO3, an important feedstock for fertilizer production, and fully regenerates MFM-520. The confinement of N2O4 inside nanopores was established at a molecular level, and the dynamic breakthrough experiments using both dry and humid NO2 gas streams verify the excellent stability and selectivity of MFM-520 and confirm its potential for precious-metal-free deNOx technologies.

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Fig. 1: Construction of MFM-520.
Fig. 2: Adsorption, selectivity, separation and stability data.
Fig. 3: Views of crystal structures.
Fig. 4: Spectroscopic data.
Fig. 5: Schematic representation of the continuous clean-up and conversion of exhaust NO2 into HNO3 using MFM-520.

Data availability

Crystallographic data for the structures reported in this article have been deposited at the Cambridge Crystallographic Data Centre under deposition numbers CCDC 1556634 (bare MOF, 298 K), 1556637 (NO2-loaded MOF, 273 K), 1556636 (NO2-loaded MOF, 283 K), 1556635 (NO2-loaded MOF, 298 K), 1556638 (NO2-loaded MOF, 313 K), 1556639 (NO2-loaded MOF, 333 K), 1556640 (NO2-loaded MOF, 353 K), 1556641 (NO2-loaded MOF, 373 K) and 1556642 (regenerated MOF, 393 K). Copies of the data can be obtained free of charge via All the other relevant data that support the findings of this study are available within the article and its Supplementary Information, or from the corresponding author upon reasonable request.


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We thank EPSRC (EP/I011870, EP/P001386, EP/K038869), ERC (AdG 742041) and the Royal Society and University of Manchester for funding, and EPSRC for funding of the EPSRC National EPR Facility at Manchester. We are especially grateful to the Advanced Light Source (ALS) and Oak Ridge National Laboratory (ORNL) for access to the beamline 11.3.1 and VISION, respectively. This research used resources of the Advanced Light Source, which is a DOE Office of Science User Facility under contract no. DE-AC02-05CH11231. Computing resources were made available through the VirtuES and the ICE-MAN projects, funded by the Laboratory Directed Research and Development program at ORNL. J.L. and X.Z. thank the China Scholarship Council for funding, and A.M.S. thanks the Russian Science Foundation (grant no. 17-73-10320) and the Royal Society of Chemistry for funding. We also thank M. A. Denecke for helpful discussions.

Author information

Authors and Affiliations



J.L. synthesized and characterized the MOF samples, and measured the adsorption isotherms. J.L. and X.H. measured and analysed the breakthrough data. S.Y., X.Z., J.L., S.J.T. and L.J.M.M. collected and analysed the in situ synchrotron X-ray diffraction data. Y.C., L.L.D. and A.J.R.-C. collected and analysed the molecular dynamics MD modelling and neutron scattering data. J.L., X.H., A.M.S., F.T. and E.J.L.M. collected and analysed the EPR data. M.S. and S.Y. directed and supervised the project and prepared the manuscript.

Corresponding authors

Correspondence to Martin Schröder or Sihai Yang.

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The authors declare no competing interests.

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Supplementary information

Supplementary Information

Supplementary methods, Figs. 1–21, Tables 1–5 and refs 1–12.

Crystallographic data

CIF for bare MOF, 298 K; CCDC reference: 1556634.

Crystallographic data

CIF for NO2-loaded MOF, 273 K; CCDC reference: 1556637.

Crystallographic data

CIF for NO2-loaded MOF, 283 K; CCDC reference: 1556636.

Crystallographic data

CIF for NO2-loaded MOF, 298 K; CCDC reference: 1556635.

Crystallographic data

CIF for NO2-loaded MOF, 313 K; CCDC reference: 1556638.

Crystallographic data

CIF for NO2-loaded MOF, 333 K; CCDC reference: 1556639.

Crystallographic data

CIF for NO2-loaded MOF, 353 K; CCDC reference: 1556640.

Crystallographic data

CIF for NO2-loaded MOF, 373 K; CCDC reference: 1556641.

Crystallographic data

CIF for regenerated MOF, 393 K; CCDC reference: 1556642.

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Li, J., Han, X., Zhang, X. et al. Capture of nitrogen dioxide and conversion to nitric acid in a porous metal–organic framework. Nat. Chem. 11, 1085–1090 (2019).

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