Adsorption of Nitrogen Dioxide in a Redox-Active Vanadium Metal–Organic Framework Material

[Image: see text] Nitrogen dioxide (NO(2)) is a toxic air pollutant, and efficient abatement technologies are important to mitigate the many associated health and environmental problems. Here, we report the reactive adsorption of NO(2) in a redox−active metal–organic framework (MOF), MFM-300(V). Adsorption of NO(2) induces the oxidation of V(III) to V(IV) centers in MFM-300(V), and this is accompanied by the reduction of adsorbed NO(2) to NO and the release of water via deprotonation of the framework hydroxyl groups, as confirmed by synchrotron X-ray diffraction and various experimental techniques. The efficient packing of {NO(2)·N(2)O(4)}(∞) chains in the pores of MFM-300(V(IV)) results in a high isothermal NO(2) uptake of 13.0 mmol g(–1) at 298 K and 1.0 bar and is retained for multiple adsorption–desorption cycles. This work will inspire the design of redox-active sorbents that exhibit reductive adsorption of NO(2) for the elimination of air pollutants.