Prolonged Hot Electron Dynamics in Plasmonic‐Metal/Semiconductor Heterostructures with Implications for Solar Photocatalysis

Abstract Ideal solar‐to‐fuel photocatalysts must effectively harvest sunlight to generate significant quantities of long‐lived charge carriers necessary for chemical reactions. Here we demonstrate the merits of augmenting traditional photoelectrochemical cells with plasmonic nanoparticles to satisfy these daunting photocatalytic requirements. Electrochemical techniques were employed to elucidate the mechanics of plasmon‐mediated electron transfer within Au/TiO 2 heterostructures under visible‐light ( λ >515 nm) irradiation in solution. Significantly, we discovered that these transferred electrons displayed excited‐state lifetimes two orders of magnitude longer than those of electrons photogenerated directly within TiO 2 via UV excitation. These long‐lived electrons further enable visible‐light‐driven H 2 evolution from water, heralding a new photocatalytic paradigm for solar energy conversion.