Real-time atomistic simulation of the Ostwald ripening of TiO₂ supported Au nanoparticles

Ostwald ripening (OR), one of the major processes of nanoparticle sintering, is critical for the rational design of functional nanomaterials. However, the atomistic mechanism of OR has not been fully understood, because the characterization of interparticle transport of atoms in real-time is challenging by either experiments or theoretical simulations. Thus, current understandings are based on ad hoc assumptions about the OR mechanism, which have never been confirmed yet at the atomic scale. Herein, we realized all-atom kinetic Monte Carlo simulation of sintering of TiO2 supported Au nanoparticles (NPs) through the OR mechanism at millisecond timescales. We demonstrated that the "semi-spherical" assumption should be removed. The OR process was a stagewise process determined by different rate-determining steps, which is in contrast to the single-stage presumption. Au dimers, rather than monomers as generally assumed, were exchanged among different NPs. Besides, we proposed a new kinetic model for describing the determining rate of OR without presumptions. This work brings deeper insights into the atomistic OR mechanism and also paves the way for real-time monitoring of catalyst sintering at the atomic scale.