Asymmetric Coordination of Single-Atom Ru Sites Achieves Efficient N(sp3)-H Dehydrogenation Catalysis for Ammonia Oxidation.

ABSTRACT

Ruthenium single-atom catalysts have great potential in ammonia-selective catalytic oxidation (NH3-SCO); however, the stable sp3 hybrid orbital of NH3 molecules makes N(sp3)-H dissociation a challenge for conventional symmetrical metallic oxide catalysts. Herein, we propose a heterogeneous interface reverse atom capture strategy to construct Ru with unique asymmetric Ru1N2O1 coordination. Ru1N2O1/CeO2 exhibits intrinsic low-temperature conversion (T100 at 160 °C) compared to symmetric coordinated Ru-based (280 °C), Ir-based (220 °C), and Pt-based (200 °C) catalysts, and the TOF is 65.4 times that of Ag-based catalysts. The experimental and theoretical studies show that there is a strong d-p orbital interaction between Ru and N atoms, which not only enhances the adsorption of ammonia at the Ru1N2O1 position but also optimizes the electronic configuration of Ru. Furthermore, the affinity of Ru1N2O1/CeO2 to water is significantly weaker than that of conventional catalysts (the binding energy of the Pd3Au1 catalyst is -1.19 eV, but it is -0.39 eV for our material), so it has excellent water resistance. Finally, the N(sp3)-H activation of NH3 requires the assistance of surface reactive oxygen species, but we found that asymmetric Ru1N2O1 can directly activate the N(sp3)-H bond without the involvement of surface reactive oxygen species. This study provides a novel principle for the rational design of the proximal coordination of active sites to achieve its optimal catalytic activity in single-atom catalysis.