Equating Cu(111) Stepped Surface and Nanoparticle Oxidation Energetics: A Multiscale Computational Study

Understanding how to inhibit oxide formation on Cu interfaces is critical to corrosion prevention and catalyst deactivation. Oxide growth on metal surfaces is supplied by diffusing O atoms, such that anisotropy in O diffusion rates along different surface structures proportionally affects their observed growth. Structural defects, such as Cu(111) surface steps and similarly faceted nanoparticles (NPs), selectively oxidize with respect to adjacent flat surfaces and differently oriented defects. Previous research suggests that differences in defect atomic coordination, attributed to dangling surface Cu bonds, yield this selective oxidation. In this study, we confirm that these oxidation preferences are conserved over morphologically distinct, equivalently oriented, Cu(111) stepped surfaces and NPs with shared edge orientations. O diffusion energetics are calculated via density functional theory, cross-validated via reactive force field molecular mechanics, and reconciled with molecular dynamics simulations. Equating surface step and NP oxidation energetics furthers the understanding of how defect structure impacts selective oxidation.