Co2 Adsorption and Activation on Auo(Co2)N−/+ (N = 1 – 3) Clusters: A Theoretical Study

Abstract

The geometric and electronic properties of AuO(CO2)n−/+ (n = 1 − 3) clusters were studied using density functional theory (DFT). Our results reveal that the coordination of the AuO unit with CO2 significantly alters CO2 geometry, generating diverse motifs. In the anionic clusters, strong Au coordination induces pronounced distortions of the CO2 moiety, resulting in CO3-like configurations. Whereas the cationic clusters retain near-linear CO2 geometries with localized charge distributions. The binding energies of both cluster types show a gradual decreasing trend, due to electrostatic stabilization. Natural population analysis (NPA) further demonstrates that the charged state and cluster size play crucial roles in modulating the electronic structure of CO2, with anions favoring covalent activation and cations maintaining CO2 linearity via electrostatic interactions. These findings enhance our fundamental understanding of CO2 activation on gold-based catalysts and provide valuable insights for the rational design of efficient catalysts for CO2 reduction and conversion processes.

Keywords: CO2-coordinated transition metal oxides, Density functional theory, geometric structure, CO2 activation