Nanoscale surface chemistry over faceted substrates: structure, reactivity and nanotemplates

Faceting is a form of self-assembly at the nanometre-scale on adsorbate-covered single-crystal surfaces, occurring when an initially planar surface converts to a "hill and valley" structure, exposing new crystal faces of nanometre-scale dimensions. Planar metal surfaces that are rough on the atomic scale, such as bcc W(111), fcc Ir(210) and hcp Re(1231), are morphologically unstable when covered by monolayer films of oxygen, or by certain other gases or metals, becoming "nanotextured" when heated to temperatures above approximately 700 K. Faceting is driven by surface thermodynamics (anisotropy of surface free energy) but controlled by kinetics (diffusion, nucleation). Surfaces can spontaneously rearrange to minimize their total surface energy (by developing facets), even if this involves an increase in surface area. In this critical review, we discuss the structural and electronic properties of such surfaces, and first principles calculations are compared with experimental observations. The utility of faceted surfaces in studies of structure sensitive reactions (e.g., CO oxidation, ammonia decomposition) and as templates for growth of metallic nanostructures is explored (122 references).