CO₂ and H₂ Activation on Zinc‐Doped Copper Clusters

Abstract

Here 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.

Spectroscopic investigation of size-dependent CO2 binding on cationic copper clusters: analysis of the CO2 asymmetric stretch

“…The in-house code is utilized to systematically generate the initial geometries for different binding modes, similar to that in our previous works. 46,63,64 The CO 2 is bound to the Cu n + ( n = 1–14) clusters in mono-(η 1 -O) or bidentate (η 2 -C, O) modes. H 2 O is bound to the most stable Cu n [CO 2 ] + structures for n = 1–10.…”