Atomically Dispersed Copper Sites in a Metal–Organic Framework for Reduction of Nitrogen Dioxide

Metal-organic framework (MOF) materials provide an excellent platform to fabricate single-atom catalysts due to their structural diversity, intrinsic porosity, and designable functionality. However, the unambiguous identification of atomically dispersed metal sites and the elucidation of their role in catalysis are challenging due to limited methods of characterization and lack of direct structural information. Here, we report a comprehensive investigation of the structure and the role of atomically dispersed copper sites in UiO-66 for the catalytic reduction of NO₂ at ambient temperature. The atomic dispersion of copper sites on UiO-66 is confirmed by high-angle annular dark-field scanning transmission electron microscopy, electron paramagnetic resonance spectroscopy, and inelastic neutron scattering, and their location is identified by neutron powder diffraction and solid-state nuclear magnetic resonance spectroscopy. The Cu/UiO-66 catalyst exhibits superior catalytic performance for the reduction of NO₂ at 25 °C without the use of reductants. A selectivity of 88% for the formation of N₂ at a 97% conversion of NO₂ with a lifetime of >50 h and an unprecedented turnover frequency of 6.1 h^-1 is achieved under nonthermal plasma activation. In situ and operando infrared, solid-state NMR, and EPR spectroscopy reveal the critical role of copper sites in the adsorption and activation of NO₂ molecules, with the formation of {Cu(I)···NO} and {Cu···NO₂} adducts promoting the conversion of NO₂ to N₂. This study will inspire the further design and study of new efficient single-atom catalysts for NO₂ abatement via detailed unravelling of their role in catalysis.