Abstract
We report the modulation of reactivity of nitrogen dioxide (NO2) in a charged metal–organic framework (MOF) material, MFM-305-CH3 in which unbound N-centres are methylated and the cationic charge counter-balanced by Cl− ions in the pores. Uptake of NO2 into MFM-305-CH3 leads to reaction between NO2 and Cl− to give nitrosyl chloride (NOCl) and NO3− anions. A high dynamic uptake of 6.58 mmol g−1 at 298 K is observed for MFM-305-CH3 as measured using a flow of 500 ppm NO2 in He. In contrast, the analogous neutral material, MFM-305, shows a much lower uptake of 2.38 mmol g−1. The binding domains and reactivity of adsorbed NO2 molecules within MFM-305-CH3 and MFM-305 have been probed using in situ synchrotron X-ray diffraction, inelastic neutron scattering and by electron paramagnetic resonance, high-field solid-state nuclear magnetic resonance and UV/Vis spectroscopies. The design of charged porous sorbents provides a new platform to control the reactivity of corrosive air pollutants.
Original language | English |
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Article number | e202302602 |
Journal | Angewandte Chemie - International Edition |
Volume | 62 |
Issue number | 28 |
DOIs | |
State | Published - Jul 10 2023 |
Funding
We thank the EPSRC (EP/I011870, EP/W014521/1, EP/V035231/1), the Royal Society and the University of Manchester for funding, and the EPSRC for funding of the EPSRC National EPR Facility at Manchester. This project has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation program (grant agreement No 742401, NANOCHEM). The UK High-Field Solid-State NMR Facility used in this research was funded by EPSRC and BBSRC (EP/T015063/1), as well as, for the 1 GHz instrument, EP/R029946/1. We are grateful to Diamond Light Source and Oak Ridge National Laboratory (ORNL) for access to Beamlines I11 and VISION (a DOE Office of Science User Facility), respectively. The computing resources were made available through the VirtuES and the ICE-MAN projects, funded by Laboratory Directed Research and Development program and Compute and Data Environment for Science (CADES) at ORNL. A.M.S. was supported by the Royal Society Newton International Fellowship. We thank the EPSRC (EP/I011870, EP/W014521/1, EP/V035231/1), the Royal Society and the University of Manchester for funding, and the EPSRC for funding of the EPSRC National EPR Facility at Manchester. This project has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation program (grant agreement No 742401, ). The UK High‐Field Solid‐State NMR Facility used in this research was funded by EPSRC and BBSRC (EP/T015063/1), as well as, for the 1 GHz instrument, EP/R029946/1. We are grateful to Diamond Light Source and Oak Ridge National Laboratory (ORNL) for access to Beamlines I11 and VISION (a DOE Office of Science User Facility), respectively. The computing resources were made available through the VirtuES and the ICE‐MAN projects, funded by Laboratory Directed Research and Development program and Compute and Data Environment for Science (CADES) at ORNL. A.M.S. was supported by the Royal Society Newton International Fellowship. NANOCHEM
Keywords
- Conversion
- Metal–Organic Framework
- Nitrogen Dioxide
- Reactivity Modulation
- Spectroscopy