Dynamic Metal-Support Interaction Dictates Cu Nanoparticle Sintering on Al$_2$O$_3$ Surfaces

Abstract

Nanoparticle sintering remains a critical challenge in heterogeneous catalysis. In this work, we present a unified deep potential (DP) model for Cu nanoparticles on three Al$_2$O$_3$ surfaces ($\gamma$-Al$_2$O$_3$(100), $\gamma$-Al$_2$O$_3$(110), and $\alpha$-Al$_2$O$_3$(0001)). Using DP-accelerated simulations, we reveal striking facet-dependent nanoparticle stability and mobility patterns across the three surfaces. The nanoparticles diffuse several times faster on $\alpha$-Al$_2$O$_3$(0001) than on $\gamma$-Al$_2$O$_3$(100) at 800 K while expected to be more sluggish based on their larger binding energy at 0 K. Diffusion is facilitated by dynamic metal-support interaction (MSI), where the Al atoms switch out of the surface plane to optimize contact with the nanoparticle and relax back to the plane as the nanoparticle moves away. In contrast, the MSI on $\gamma$-Al$_2$O$_3$(100) and on $\gamma$-Al$_2$O$_3$(110) is dominated by more stable and directional Cu-O bonds, consistent with the limited diffusion observed on these surfaces. Our extended long-time MD simulations provide quantitative insights into the sintering processes, showing that the dispersity of nanoparticles (the initial inter-nanoparticle distance) strongly influences coalescence driven by nanoparticle diffusion. We observed that the coalescence of Cu$_{13}$ nanoparticles on $\alpha$-Al$_2$O$_3$(0001) can occur in a short time (10 ns) at 800 K even with an initial inter-nanoparticle distance increased to 30 \r{A}, while the coalescence on $\gamma$-Al$_2$O$_3$(100) is inhibited significantly by increasing the initial inter-nanoparticle distance from 15 \r{A} to 30 \r{A}. These findings demonstrate that the dynamics of the supporting surface is crucial to understanding the sintering mechanism and offer guidance for designing sinter-resistant catalysts by engineering the support morphology.