Computational Appraisal of Silver Nanocluster Evolution on Epitaxial Graphene: Implications for CO Sensing

[Image: see text] Early stages of silver nucleation on a two-dimensional (2D) substrate, here, monolayer epitaxial graphene (MEG) on SiC, play a critical role in the formation of application-specific Ag nanostructures. Therefore, it is of both fundamental and practical importance to investigate the growth steps when Ag adatoms start to form a new phase. In this work, we exploit density functional theory to study the kinetics of early-stage nuclei Ag(n) (n = 1–9) assembly of Ag nanoparticles on MEG. We find that the Ag(1) monomer tends to occupy hollow site positions of MEG and interacts with the surface mainly through weak dispersion forces. The pseudoepitaxial growth regime is revealed to dominate the formation of the planar silver clusters. The adsorption and nucleation energies of Ag(n) clusters exhibit evident odd–even oscillations with cluster size, pointing out the preferable adsorption and nucleation of odd-numbered clusters on MEG. The character of the interaction between a chemisorbed Ag(3) cluster and MEG makes it possible to consider this trimer as the most stable nucleus for the subsequent growth of Ag nanoparticles. We reveal the general correlation between Ag/MEG interaction and Ag–Ag interaction: with increasing cluster size, the interaction between Ag adatoms increases, while the Ag/MEG interaction decreases. The general trend is also supported by the results of charge population analysis, according to which the average charge per Ag adatom in a Ag(n) cluster demonstrates a drastic decrement with cluster size increase. 2D–3D structural transition in Ag(n) clusters was investigated. We anticipate that the present investigation is beneficial by providing a better understanding of the early-stage nucleation of Ag nanoparticles on MEG at the atomic scale. Specific interaction between odd-numbered Ag clusters preadsorbed onto the MEG surface and carbon monoxide (CO) as well as clusters’ stability at 300 K is discussed in terms of sensing applications.