Plasmon-Induced CO₂ Conversion on Al@Cu₂O: A DFT Study

In plasmonic catalysis, localized surface plasmons can be leveraged to drive chemical reactions. This approach is promising for catalyzing many challenging reactions at relatively low temperatures and pressures. We apply density functional theory calculations to provide an insight into the mechanism of plasmon-induced direct CO₂ dissociation on an Al@Cu₂O core–shell structure, which was observed in a previous experimental study. We show that the interaction of Cu₂O with CO₂ results in accessible antibonding states of the adsorbed CO₂ in the range of visible light. Although the intrinsic activation barrier for direct CO₂ dissociation is as high as 3.6 eV, we find that an effective reaction barrier of CO₂ dissociation under photon excitation could be reduced by 2 eV. We also show that the charge transfer is more pronounced in the final state of dissociation due to the strong hybridization of the dissociated species with Cu₂O. These results thus provide an explanation for the visible-light-induced direct CO₂ dissociation at relatively low temperatures and under ambient pressure. The findings also show the promising role of plasmonic catalysis in mitigating carbon emission.