Abstract
Nanoparticle and thin film surface plasmons are highly sensitive to electrochemically induced dielectric changes. We exploited this sensitivity to detect reversible electrochemical potential-driven anion adsorption by developing single-particle plasmon voltammetry (spPV) using plasmonic nanoparticles. spPV was used to detect sulfate electroadsorption to individual Au nanoparticles. By comparing both semiconducting and metallic thin film substrates with Au nanoparticle monomers and dimers, we demonstrated that using Au film substrates improved the signal in detecting sulfate electroadsorption and desorption through adsorbate modulated thin film conductance. Using single-particle surface plasmon spectroscopic techniques, we constructed spPV to sense sulfate, acetate, and perchlorate adsorption on coupled Au nanoparticles. spPV extends dynamic spectroelectrochemical sensing to the single-nanoparticle level using both individual plasmon resonance modes and total scattering intensity fluctuations.