It is vital to differentiate catalytic properties between cationic and metallic single atoms at the atomic level. To achieve this, we fabricated well-defined cationic Ni atoms snugged in and metallic Ni atoms supported on monolayered CuO. The Ni cations are chemically inert for CO adsorption even at 70 K but highly active toward O2 dissociation at room temperature. The adsorbed O atoms are active to oxidize incoming CO molecules from the gas phase into CO2, which follows the Eley–Rideal mechanism, in contrast to the Mars–van Krevelen mechanism on CuO-monolayer-supported metallic Ni atoms as well as our previously reported Au and Pt model catalysts. This study helps understand the chemistry of a supported single-metal cation, which is of great importance in heterogeneous catalysis.
