Screening of transition metal doped copper clusters for CO2activation

Abstract

Activation of CO2is the first step towards its reduction to more useful chemicals. Here we systematically investigate the CO2activation mechanism on Cu3X (X is a first-row transition metal atom) using density functional theory computations. The CO2adsorption 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 CO2dissociation efficiency. Our calculations reveal that early transition metal-doped (Sc, Ti, V) clusters exhibit a high CO2adsorption 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.