Abstract

Localized surface plasmons (LSP) on faceted surfaces of gold nanoparticles enable carbon monoxide disproportionation to be driven at room temperature. In order to expand the known surfaces that catalyze this reaction, we explore the adsorption of carbon monoxide at top, long bridge, short bridge, and hole sites on gold (100), (110), (111), (211), and (311) faceted surfaces, as well as the reaction barriers for disproportionation at the lowest energy adsorption site on each surface and edges between two (311) surfaces and (100) and (110) surfaces. Generally, the less atomically dense, higher index facets promote both good adsorption and reactivity, and the edges show lower barriers for disproportionation. For most of the explored surfaces, adsorption directly on top of a gold atom is most favorable. The lowest activation energy for carbon monoxide disproportionation to amorphous carbon and carbon dioxide is predicted for two carbon monoxides adsorbed on top of atoms on the (311)/(311) edge.