Journal of the American Chemical Society, Vol.136, No.30, 10783-10789, 2014
Solution Voltammetry of 4 nm Magnetite Iron Oxide Nanoparticles
The voltammetry of solution-dispersed magnetite iron oxide Fe3O4 nanoparticles is described. Their currents are controlled by nanoparticle transport rates, as shown with potential step chronoamperometry and rotated disk voltammetry. In pH 2 citrate buffer with added NaClO4 electrolyte, solution cyclic voltammetry of these nanoparticles (average diameter 4.4 +/- 0.9 nm, each containing ca. 30 Fe sites) displays an electrochemically irreversible oxidation with E-PEAK at ca. +0.52 V and an irreversible reduction with E-PEAK at ca. +0.2 V vs Ag/AgCl reference electrode. These processes are presumed to correspond to the formal potentials for one-electron oxidation of Fe(II) and reduction of Fe(III) at their different sites in the magnetite nanoparticle structure. The heterogeneous electrode reaction rates of the nanoparticles very slow, in the 10(-5) cm/s range. The nanoparticles are additionally characterized by a variety of tools, e.g., TEM, UV/vis, and XPS spectroscopies.