Modulating the Structural Dynamics and Catalytic Properties of a Cu Cluster via CO-Mediated Spatial Confinement

Spatial confinement provides a powerful approach to tune the catalytic properties of metal clusters by creating unique nanoscale environments around them. However, the dynamic structural evolution of the confined clusters covered by high-coverage adsorbates and the consequent impact on the catalytic properties remain poorly understood. In this work, using density functional theory calculations and <i>ab initio</i> molecular dynamics simulations, we demonstrate that the CO molecules adsorbed on an encapsulated Cu₁₈ cluster can mediate interactions between the (17, 0) zigzag carbon nanotube (CNT) inner wall and Cu₁₈, which significantly regulates the structural dynamics and reactivity of the confined cluster. It is found that the Cu cluster in the CNT exhibits reduced Cu-Cu coordination numbers and recurrent multiadsorption structures of CO, both of which are absent in the corresponding cluster on the open space of graphene. The unique structural features of the encapsulated Cu cluster in the CNT can further promote a C-C coupling reaction. Our work provides a new adsorbate-assisted approach to tune the structural dynamics of confined clusters and may open up new opportunities to improve the performance of confined catalysts.