CO and H Activation on Zinc-Doped Copper Clusters.

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