Shape-dependent oxidation rates of nano-structured silver particles

Reactive molecular dynamics is used to investigate the oxidation of anisotropic silver nanoparticles (nano-Ag) of various shapes, including sphere, cube, disk, cylinder, triangle, and pyramid. The effect of the nano-Ag initial morphology on their stability and composition during oxidation is quantified. Surface oxidation at 600 K leads to the formation of a core-shell structure for all nano-Ag shapes. The surface composition of facet orientations of pristine nano-Ag can be correlated with particle stability due to their different surface energies and oxygen reactivity. In particular, pyramid and triangular nano-Ag, having a high surface fraction of (110) facets, are more prone to morphological changes upon oxidation and loss of their crystallinity, compared to nanospheres and nanocubes, which exhibit the highest stability among all shapes, attributed to the large fraction of highly coordinated atoms. Spherical and cubic nano-Ag oxidize faster, owing to their large surface fractions of (100) and (111) facets, which are more reactive than (110) ones. Understanding the effect of surface crystal structure and shape of anisotropic nano-Ag can improve the design of superior metal oxide nanomaterials with desired characteristics.