Groove-Confined Cobalt Catalyst for Low-Temperature CO2 Activation

CO₂ activation is of great significance for resource utilization and environmental protection, but remains a major challenge. Here, we present a study of CO₂ activation and dissociation on a single crystal Co(101̅0) surface below 150 K via combined surface techniques and DFT calculations. Our study reveals that the groove site of the Co(101̅0) surface provides an ideal anchor for a surface-confined bent CO₂, showing tridentate coordination with the surface. With this understanding, a cobalt nanocrystal catalyst containing groove sites was developed, high activity and high selectivity for conversion of CO₂ to CO by the reverse water–gas shift reaction were acquired. The nanocrystal catalyst with these groove sites appears to be much more active in comparison to the catalysts without such sites. This study provides key insights into the active sites and activation configuration for moderate-condition CO₂ activation and precise atomic-level design of confinement-controlled heterogeneous catalysts.