Elucidation of Cu–Zn Surface Alloying on Cu(997) by Machine-Learning Molecular Dynamics

[Image: see text] The Cu–Zn surface alloy has been extensively involved in the investigation of the true active site of Cu/ZnO/Al(2)O(3), the industrial catalyst for methanol synthesis which remains under controversy. The challenge lies in capturing the interplay between the surface and reaction under operating conditions, which can be overcome given that the explicit dynamics of the system is known. To provide a better understanding of the dynamic of Cu–Zn surface at the atomic level, the structure and the formation process of the Cu–Zn surface alloy on Cu(997) were investigated by machine-learning molecular dynamics (MD). Gaussian process regression aided with on-the-fly learning was employed to build the force field used in the MD. The simulation reveals atomistic details of the alloying process, that is, the incorporation of deposited Zn adatoms to the Cu substrate. The surface alloying is found to start at upper and lower terraces near the step edge, which emphasize the role of steps and kinks in the alloying. The incorporation of Zn at the middle terrace was found at the later stage of the simulation. The rationalization of alloying behavior was performed based on statistics and barriers of various elementary events that occur during the simulation. It was observed that the alloying scheme at the upper terrace is dominated by the confinement of Zn step adatoms by other adatoms, highlighting the importance of step fluctuations in the alloying process. On the other hand, the alloying scheme at the lower terrace is dominated by direct exchange between the Zn step adatom and the Cu atom underneath. The alloying at the middle terrace is dominated by the wave deposition mechanism and deep confinement of Zn adatoms. The short propagation of alloyed Zn in the middle terrace was observed to proceed by means of indirect exchange instead of local exchange as proposed in the previous scanning tunneling microscopy (STM) observation. The comparison of migration rate and activation energies to the result of STM observation is also made. We have found that at a certain distance from the surface, the STM tip significantly affects the elementary events such as vacancy formation and direct exchange.