CO2 and H2 Activation on Zinc‐Doped Copper Clusters

Abstract

AbstractHere we systematically investigate the CO2 and H2 activation and dissociation on small CunZn0/+ (n=3–6) clusters using Density Functional Theory. We show that Cu6Zn is a superatom, displaying an increased HOMO‐LUMO gap and is inert towards CO2 or H2 activation or dissociation. While other neutral clusters weakly activate CO2, the cationic clusters preferentially bind the CO2 in monodentate nonactivated way. Notably, Cu4Zn allows for the dissociation of activated CO2, whereas larger clusters destabilize all activated CO2 binding modes. Conversely, H2 dissociation is favored on all clusters examined, except for Cu6Zn. Cu3Zn+ and Cu4Zn, favor the formation of formate through the H2 dissociation pathway rather than CO2 dissociation. These findings suggest the potential of these clusters as synthetic targets and underscore their significance in the realm of CO2 hydrogenation.