Less Noble or More Noble: How Strain Affects the Binding of Oxygen on Gold

Many heterogeneous catalysts exploit strained active layers to modulate reactivity and/or selectivity. It is therefore significant that density functional theory, as well as experimental approaches, find that tensile strain makes the gold surface more binding for oxygen, in other words, less noble. We show that this behavior does not apply when re-structuring of the gold surface is allowed to occur simultaneously with the adsorption of oxygen. Insitu cantilever-bending studies show the surface stress to increase when oxygen species adsorb on a (111)-textured gold surface in aqueous H2SO4. This implies a positive sign of the electrocapillary coupling parameter and, hence, a trend for weaker oxygen binding in response to tensile strain. These conflicting findings indicate that different electrosorption processes, and specifically oxygen species adsorption on the bulk-terminated surface, exhibit fundamentally different coupling between the chemistry and the mechanics of the surface.