Dual-Plasmonic Gold@Copper Sulfide Core-Shell Nanoparticles: Phase-Selective Synthesis and Multimodal Photothermal and Photocatalytic Behaviors

Although the intriguing plasmonic properties of noble metal nanoparticles originate from the collective oscillations of free electrons in the conduction band, nanoparticles of doped semiconductors may also exhibit metal-like, plasmonic features that are dictated by the resonantly excited free hole oscillations in the valence band. Here, we combine Au, a representative free electron metal, with copper sulfides, a class of plasmonic p-type semiconductors, in a core-shell nanoparticle geometry to construct dualplasmonic hetero-nanostructures displaying unique multiplex optical characteristics dominated by plasmonic hole oscillations in the semiconductor shells, plasmonic electron oscillations in the metallic cores, and interband electronic transitions from the valence to conduction bands. Through deliberately designed colloidal synthesis, we are able to selectively grow nanoshells comprising copper sulfides of specifically targeted crystalline phases and Cu/S stoichiometries, such as covellite (CuS), digenite (Cu1.8S), and nonstoichiometric Cu2-xS, on the surfaces of Au nanoparticle cores. Our synthetic approach enables us not only to finely control the core and shell dimensions but also to systematically adjust the free hole concentrations in the semiconductor shells, which forms the keystone for the fine tuning of multiple optical resonance modes supported by these hybrid hetero-nanostructures. The dual- plasmonic Aupcopper sulfide core-shell nanoparticles exhibit unique multimodal photothermal and photocatalytic behaviors upon selective photoexcitations of different optical transitions at their characteristic resonant frequencies, allowing us to quantitatively evaluate and rigorously compare the intrinsic photothermal and photocatalytic efficacies of multiple types of hot charge carriers, all photoexcited in the same hybrid nanoparticles but with distinct photophysical origins, excited-state lifetimes, energy distributions, and transfer pathways.