Abstract
Plasmonic nanocavities offer exceptional confinement of light, making them effective for energy conversion applications. However, limitations with stability, materials, and chemical activity have impeded their practical implementation. Here we integrate ultrathin palladium (Pd) metal films from sub- to few- atomic monolayers inside plasmonic nanocavities using underpotential deposition. Despite the poor plasmonic properties of bulk Pd in the visible region, minimal loss in optical field enhancement is delivered along with Pd chemical enhancement, as confirmed by ab initio calculations. Such synergistic effects significantly enhance photocatalytic activity of the plasmonic nanocavities as well as photostability by suppressing surface atom migration. We show the atomic alchemical-glazing approach is general for a range of catalytic metals that bridge plasmonic and chemical catalysis, yielding broad applications in photocatalysis for optimal chemical transformation.