Screening of transition metal doped copper clusters for CO2 activation

Abstract

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.