Clustering-Evolved Frontier Orbital for Low-Temperature CO 2 Dissociation.

In this study, single Ni 2 clusters (two Ni atoms bridged by a lattice oxygen) are successfully synthesized on monolayered CuO. They exhibit a remarkable activity toward low-temperature CO 2 thermal dissociation, in contrast to cationic Ni atoms that nondissociatively adsorb CO 2 and metallic Ni ones that are chemically inert for CO 2 adsorption. Density functional theory calculations reveal that the Ni 2 clusters can significantly alter the spatial symmetry of their unoccupied frontier orbitals to match the occupied counterpart of the CO 2 molecule and enable its low-temperature dissociation. This study may help advance single-cluster catalysis and exploit the unexcavated mechanism for low-temperature CO 2 activation.