Controlling the nucleation and growth of ultrasmall metal nanoclusters with MoS₂ grain boundaries

The stabilization of supported nanoclusters is critical for different applications, including catalysis and plasmonics. Herein we investigate the impact of MoS₂ grain boundaries (GBs) on the nucleation and growth of Pt NCs. The optimum atomic structure of the metal clusters is obtained using an adaptive genetic algorithm that employs a hybrid approach based on atomistic force fields and density functional theory. Our findings show that GBs stabilize the NCs up to a cluster size of nearly ten atoms, and with larger clusters having a similar binding to the pristine system. Notably, Pt monomers are found to be attracted to GB cores achieving 60% more stabilization compared to the pristine surface. Furthermore, we show that the nucleation and growth of the metal seeds are facile with low kinetic barriers, which are of similar magnitude to the diffusion barriers of metals on the pristine surface. The findings highlight the need to engineer ultrasmall NCs to take advantage of enhanced stabilization imparted by the GB region, particularly to circumvent sintering behavior for high-temperature applications.