Single-particle spectroelectrochemistry: electrochemical tuning of plasmonic properties via mercury amalgamation in mesoporous silica coated gold nanorods without structural deformation

Abstract

This paper elucidates the mercury (Hg) amalgamation induced by electrochemical reduction on gold nanorods coated with mesoporous silica shell (AuNRs@mSiO₂) using single-particle spectroelectrochemistry. First, the silica shell significantly enhanced the structural stability of AuNR cores after Hg amalgamation with the application of linear sweep voltages (LSVs). Thus, we were able to focus on the spectral changes of AuNRs@mSiO₂ induced by the deposition of Hg without the disturbance of structural deformation, which also strongly affects localized surface plasmon resonance (LSPR) properties. Second, following the application of LSVs in the presence of Hg²⁺, a remarkable blueshift of the LSPR peak was observed, caused by the lowering of the work function due to the Hg adsorption, donating electron density to Au. Furthermore, the LSPR linewidth also dramatically increased after the Hg deposition with LSV. Lastly, the evolution of the Hg amalgamation process was directly observed by monitoring real-time LSPR peaks and LSPR linewidth shifts of a single AuNRs@mSiO₂ in the Hg solution according to the application of the electrochemical potential. Moreover, the results showed the possibility of the in situ tuning of the LSPR properties of AuNRs@mSiO₂ by Hg deposition via electrochemical potential manipulations without the disturbance of the structural variations of AuNR cores.