Modulation of Uptake and Reactivity of Nitrogen Dioxide in Metal‐Organic Framework Materials
Zi Wang, Alena M. Sheveleva, Daniel Lee, Yinlin Chen, Dinu Iuga, W. Trent Franks, Yujie Ma, Jiangnan Li, Lei Li, Yongqiang Cheng, Luke L. Daemen, Sarah J. Days, Anibal J. Ramirez‐Cuesta, Bing Han, Alexander S. Eggeman, Eric J. L. McInnes, Floriana Tuna, Sihai Yang⧫, Martin Schröder
Abstract
Abstract We report the modulation of reactivity of nitrogen dioxide (NO 2 ) in a charged metal–organic framework (MOF) material, MFM‐305‐CH 3 in which unbound N‐centres are methylated and the cationic charge counter‐balanced by Cl − ions in the pores. Uptake of NO 2 into MFM‐305‐CH 3 leads to reaction between NO 2 and Cl − to give nitrosyl chloride (NOCl) and NO 3 − anions. A high dynamic uptake of 6.58 mmol g −1 at 298 K is observed for MFM‐305‐CH 3 as measured using a flow of 500 ppm NO 2 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 NO 2 molecules within MFM‐305‐CH 3 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.