Clustering-Evolved Frontier Orbital for Low-Temperature CO2 Dissociation

In this study, single Ni-2 clusters (two Niatoms bridgedby a lattice oxygen) are successfully synthesized on monolayered CuO.They exhibit a remarkable activity toward low-temperature CO2 thermal dissociation, in contrast to cationic Ni atoms that nondissociativelyadsorb CO2 and metallic Ni ones that are chemically inertfor CO2 adsorption. Density functional theory calculationsreveal that the Ni-2 clusters can significantly alter thespatial symmetry of their unoccupied frontier orbitals to match theoccupied counterpart of the CO2 molecule and enable itslow-temperature dissociation. This study may help advance single-clustercatalysis and exploit the unexcavated mechanism for low-temperatureCO(2) activation.