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

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.