Mixed-valence metal oxide nanoparticles as electrochemical half-cells: Substituting the Ag/AgCl of reference electrodes by CeO2-x nanoparticles

Abstract

Cations of mixed valence at surfaces of metal oxide nanoparticles constitute electrochemical half-cells, with potentials intermediate between those of the dissolved cations and those in the solid. When only cations at surfaces of the particles are electrochemically active, the ratio of electrochemically active/all cations is ∼0.1 for 15 nm diameter CeO 2-x particles. CeO2-x nanoparticle-loaded hydrogel films on printed carbon and on sputtered gold constitute reference electrodes having a redox potential similar to that of Ag/AgCl in physiological (0.14 M) saline solutions. In vitro the characteristics of potentially subcutaneously implantable glucose monitoring sensors made with CeO2-x nanoparticle reference electrodes are undistinguishable from those of sensors made with Ag/AgCl reference electrodes. Cerium is 900 times more abundant than silver, and commercially produced CeO2-x nanoparticle solutions are available at prices well below those of the Ag/AgCl pastes used in the annual manufacture of ∼109 reference electrodes of glucose monitoring strips for diabetes management. © 2012 American Chemical Society.