Screening of transition metal doped copper clusters for CO2 activation.

Activation of CO2 is the first step towards its reduction to more useful chemicals. Here we systematically investigate the CO2 activation mechanism on Cu3X (X is a first-row transition metal atom) using density functional theory computations. The CO2 adsorption energies and the activation mechanisms depend strongly on the selected dopant. The dopant electronegativity, the HOMO–LUMO gap and the overlap of the frontier molecular orbitals control the CO2 dissociation efficiency. Our calculations reveal that early transition metal-doped (Sc, Ti, V) clusters exhibit a high CO2 adsorption energy, a low activation barrier for its dissociation, and a facile regeneration of the clusters. Thus, early transition metal-doped copper clusters, particularly Cu3Sc, may be efficient catalysts for the carbon capture and utilization process.