Light Driven Mechanism of Carbon Dioxide Reduction Reaction to Carbon Monoxide on Gold Nanoparticles: A Theoretical Prediction

Insightful understanding of the light driven CO₂ reduction reaction (CO₂RR) mechanism on gold nanoparticles is one of the important issues in the plasmon mediated photocatalytic study. Herein, time-dependent density functional theory and reduced two-state model are adopted to investigate the photoinduced charge transfer in interfaces. According to the excitation energy and orbital coupling, the light driven mechanism of CO₂RR on gold nanoparticles can be described as follows: the light induces electron excitation and then transfers to the physisorbed CO₂, and CO₂ can relax to a bent structure adsorbed on gold nanoparticles, and the adsorbed C-O bonds are dissociated finally. Moreover, our calculated results demonstrate that the s, p, and d electron excitations of gold nanoparticles are the major contribution for the CO₂ adsorption and the C-O dissociation process, respectively. This work would promote the understanding of the light driven electron transfer and photocatalytic CO₂RR on the noble metal.