Enhanced dual plasmonic photocatalysis through plasmonic coupling in eccentric noble metal-nonstoichiometric copper chalcogenide hetero-nanostructures

The extension of plasmonics to materials beyond the conventional noble metals opens up a novel and exciting regime after the inspiring discovery of characteristic localized surface plasmon resonances (LSPRs) in doped semiconductor nanocrystals originating from the collective oscillations of free holes in the valence band. We herein prepare colloidal monodisperse eccentric dual plasmonic noble metal-nonstoichiometric copper chalcogenide (Au@Cu2−xSe) hybrid hetero-nanostructures with precisely controlled semiconductor shell size and two tunable LSPRs in both visible (VIS) and near-infrared (NIR) regions associated with Au and Cu2−xSe, respectively. Through systematic evaluations of the photocatalytic performance of Au@Cu2−xSe upon sole NIR and dual VIS + NIR simultaneous excitations, we are capable of unambiguously elucidating the role of plasmonic coupling between two dissimilar building blocks on the accelerated photocatalytic reactions with greater rate constants from both experimental and computational perspectives. The significantly enhanced strength of the electromagnetic field arising from efficient plasmonic coupling under the excitation of two LSPRs results in the superior activities of dual plasmonic Au@Cu2−xSe in photocatalysis. The new physical and chemical insights gained from this work provide the keystone for the rational design and construction of high-quality dual- or even multi-plasmonic nano-systems with optimized properties for widespread applications ranging from photocatalysis to molecular spectroscopies.