Atomically-dispersed copper sites in a metal-organic framework for reduction of nitrogen dioxide

Yujie Ma, Xue Han, Shaojun Xu, Zi Wang, Weiyao Li, Ivan Da Silva, Sarayute Chansai, Daniel Lee, Yichao Zou, Marek Nikiel, Pascal Manual, Alena M. Sheveleva, Floriana Tuna, Eric Mcinnes, Yongqiang Cheng, Svemir Rudić, Anibal J. Ramirez-Cuesta, Sarah Haigh, Chris Hardacre, Martin SchroderSihai Yang

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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 atomi-cally-dispersed metal sites and elucidation of their role in catalysis are challenging due to limited methods of characteri-zation 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 mi-croscopy, electron paramagnetic resonance spectroscopy and inelastic neutron scattering, and their location identified by neutron powder diffraction and solid-state nuclear magnetic resonance spectroscopy. The Cu/UiO-66 catalyst exhibits superior catalytic performance for reduction of NO2 at 25 °C without the use of reductants. A selectivity of 88% for the formation of N2 at 97% conversion of NO2 with a lifetime of >50 h and an unprecedented turnover frequency of 6.1 h-1 is achieved under non-thermal 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.
Original languageEnglish
JournalJournal of the American Chemical Society
Publication statusAccepted/In press - 1 Jun 2021

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