Electrochemical aspects of coinage metal nanoparticles for catalysis and spectroscopy

Abstract

Down scaling bulk materials can cause colloidal systems to evolve into microscopically dispersed insoluble particles. Herein, we describe the interesting applications of coinage metal nanoparticles (MNPs) as colloid dispersions especially gold and silver. The rich plasmon bands of gold and silver in the visible range are elaborated using the plasmon resonance and redox potential values of grown metal microelectrode (GME). The gradation of their standard reduction potential values (E⁰), as evaluated from the Gibbs free energy change for bulk metal, is ascribed to the variation in their size. Also, the effect of nucleophiles in the electrolytic cell with metal nanoparticles (MNPs) is described. The nucleophile-guided reduction potential value is considered, which is applicable even for bulk noble metals. Typically, a low value (as low as E⁰ = +0.40 V) causes the oxidation of metals at the O₂ (air)/H₂O interface. Under this condition, the oxidation of noble metal particles and dissolution of the noble metal in water are demonstrated. Thus, metal dissolution as a function of the size of metal nanoparticles becomes eventful and demonstrable with the addition of a surfactant to the solution. Interestingly, the reversal of the nobility of gold (Au) and silver (Ag) microelectrodes at the water/electrode interface is confirmed from the evolution of normal and inverted ‘core–shell’ structures, exploiting visible spectrophotometry and surface-enhanced Raman scattering (SERS) analysis. Subsequently, the effect of the size, shape, and facet- and support-selective catalysis of gold nanoparticles (NPs) and the effect of incident photons on current conversion without an applied potential are briefly discussed. Finally, the synergistic effect of the emissive behaviour of gold and silver clusters is productively exploited.