Undercoordinated Active Sites on 4H Gold Nanostructures for CO₂ Reduction

Electroreduction of CO₂ is a promising approach toward artificial carbon recycling. The rate and product selectivity of this reaction are highly sensitive to the surface structures of electrocatalysts. We report here 4H Au nanostructures as advanced electrocatalysts for highly active and selective reduction of CO₂ to CO. Au nanoribbons in the pure 4H phase, Au nanorods in the hybrid 4H/fcc phase, and those in the fcc phase are comparatively studied for the electroreduction of CO₂. Both the activity and selectivity for CO production were found to exhibit the trend 4H-nanoribbons > 4H/fcc-nanorods > fcc-nanorods, with the 4H-nanoribbons achieving >90% Faradaic efficiency toward CO. Electrochemical probing and cluster expansion simulations are combined to elucidate the surface structures of these nanocrystals. The combination of crystal phase and shape control gives rise to the preferential exposure of undercoordinated sites. Further density functional theory calculations confirm the high reactivity of such undercoordinated sites.