Theoretical Insights into Synergistic Effects at Cu/TiC Interfaces for Promoting CO₂ Activation

The adsorption behaviors of CO₂ at the Cu_n/TiC­(001) interfaces (n = 1–8) have been investigated using the density functional theory method. Our results reveal that the introduction of copper clusters on a TiC surface can significantly improve the thermodynamic stability of CO₂ chemisorption. However, the most stable adsorption site is sensitive to the size and morphology of Cu_n particles. The interfacial configuration is the most stable structure for copper clusters with small (n ≤ 2) and large (n ≥ 8) sizes, in which both Cu particles and TiC support are involved in CO₂ activation. In such a case, the synergistic behavior is associated with the ligand effect introduced by directly forming adsorption bonds with CO₂. For those Cu_n clusters with a medium size (n = 3–7), the configuration where CO₂ adsorbs solely on the exposed hollow site constructed by Cu atoms at the interface shows the best stability, and the charger transfer becomes the primary origin of the synergistic effect in promoting CO₂ activation. Since the most obvious deformation of CO₂ is observed for the TiC(001)-surface-supported Cu₄ and Cu₇ particles, copper clusters with specific sizes of n = 4 and 7 exhibit the best ability for CO₂ activation. Furthermore, the kinetic barriers for CO₂ dissociation on Cu₄- and Cu₇-supported TiC surfaces are determined. The findings obtained in this work provide useful insights into optimizing the Cu/TiC interface with high catalytic activation of CO₂ by precisely controlling the size and dispersion of copper particles.