Noble metal nanostructures can efficiently harvest electromagnetic radiation, which, in turn, is used to generate localized surface plasmon resonances. Surface plasmons decay, producing hot carriers, that is, short-lived species that can trigger chemical reactions on metallic surfaces. However, noble metal nanostructures catalyze only a very small number of chemical reactions. This limitation can be overcome by coupling such nanostructures with catalytic-active metals. Although the role of such catalytically active metals in plasmon-driven catalysis is well-understood, the mechanistics of a noble metal antenna in such chemistry remains unclear. In this study, we utilize tip-enhanced Raman spectroscopy, an innovative nanoscale imaging technique, to investigate the rates and yields of plasmon-driven reactions on mono- and bimetallic gold- and silver-based nanostructures. We found that silver nanoplates (AgNPs) demonstrate a significantly higher yield of 4-nitrobenzenehtiol to p,p'-dimercaptoazobisbenzene (DMAB) reduction than gold nanoplates (AuNPs). We also observed substantially greater yields of DMAB on silver-platinum and silver-palladium nanoplates (Ag@PtNPs and Ag@PdNPs) compared to their gold analogues, Au@PtNPs and Au@PdNPs. Furthermore, Ag@PtNPs exhibited enhanced reactivity in 4-mercatophenylmethanol to 4-mercaptobenzoic acid oxidation compared to Au@PtNPs. These results showed that silver-based bimetallic nanostructures feature much greater reactivity compared to their gold-based analogues.
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