Long-Range Oxygen Spillover at the Cu/CeO₂ Interface

Reverse oxygen spillover (ROS) from ceria (CeO₂) to supported metal species, driven by strong metal-support interactions, profoundly impacts not only their catalytic efficacy but also the structural stability, dispersion, and electronic characteristics of the metal active sites. Herein, we for the first time observed a long-range dynamic ROS phenomenon at the interface of Cu/CeO₂ catalysts by means of first-principles calculations and ab initio and deep-potential molecular dynamics (DPMD) simulations. The ROS process is initiated by interfacial lattice oxygen transfer to Cu species, followed by the sequential migration of adjacent O atoms through oxygen vacancies, resulting in the progressive oxidation of supported Cu species. In addition, DPMD simulations reveal the persistence of the long-range ROS process over larger time and spatial scales, with larger Cu nanoparticles exhibiting faster and more extensive ROS. These findings provide mechanistic insights into the importance of long-range ROS behaviors in the preparation of oxide-supported metal catalysts.