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

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/TiO2 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 TiO2 via UV excitation. These long‐lived electrons further enable visible‐light‐driven H2 evolution from water, heralding a new photocatalytic paradigm for solar energy conversion. Harvesting hot electrons: Plasmon‐mediated electron transfer (PMET) in plasmonic (Au/TiO2) photoanodes provides a unique pathway for procuring excited‐state electrons that exhibit lifetimes commensurate with the prolonged timescales required for solar photochemistry. These long‐lived electrons were harnessed for visible‐light‐driven hydrogen evolution from water (see picture).