Electrochemical Surface Plasmon Resonance: Basic Formalism and Experimental Validation

摘要

A quantitative formalism of electrochemical surface plasmonnresonance (EC-SPR) was developed for studyingnelectrochemical reactions. The EC-SPR signal from thenreactions was found to be a convolution function ofnelectrochemical current, and therefore, EC-SPR is anpowerful tool that can provide information similar to thenconventional current-based electrochemical techniques.nAs an example, potential-sweep EC-SPR was analyzed inndetails and was found to provide a new way to measurenconvolution voltammetry without the need of numericalnintegration. In addition to the benefits provided by thenconventional convolution voltammetry, the EC-SPR hasnseveral unique advantages, including (1) spatial resolutionnthat is particularly attractive for studying heterogeneousnreactions, (2) optical properties of the reactions speciesnthat may assist identification of reaction mechanisms, andn(3) high surface sensitivity for studying surface bindingnof the reaction species. Experiments and numericalnsimulations were carried out for a model system, hexaammineruthenium(nIII) chloride. The simultaneously measurednelectrochemical current and SPR response confirmednthe relationship between the two quantities, andnthe numerical simulations were in excellent agreementnwith the measurements.