Study of the formation and quick growth of thick oxide films using platinum nanoelectrodes as a model electrocatalyst.

Abstract

We report a study of the formation and quick growth of thick films of platinum oxide on platinum nanoelectrodes at low anodic potentials. Here, structurally well-defined platinum nanoelectrodes are used as a model platform for nanoscale platinum electrocatalysts. Platinum films are formed on the surface of the nanoelectrode upon application of a constant anodic potential in an acidic environment for an extended time period. A current spike is initially observed, which is attributed to capacitance charging, the oxidation of water, and the initial oxidation of the platinum surface. A finite residual current follows the initial current spike, which is composed of both water oxidation and the oxidation of platinum metal concealed beneath the growing oxide layer. These films are observed to be structurally irreversible, grow to be relatively thick, and protrude out of the glass insulating material encasing the nanoelectrode due to the added volume of the oxygen incorporated into the growing platinum oxide film. Once reduced, the platinum metal remains protruding out of the glass, and its presence is confirmed by both SEM imaging and cyclic voltammetry. Steady-state voltammetric data shows a finite increase in the diffusion-limited faradaic current of the nanoelectrode, relative to the initial steady-state current, after the oxidation/reduction of the platinum which is due to an increased area of the protruding platinum metal. A minimum apparent rate of ∼1.2 nm/min can be calculated for the growth of the platinum oxide film. The use of platinum nanoelectrodes has shown several distinct advantages in this study, including better control of the size and morphology of the individual electrocatalysts, the ability to image using electron microscopy, and the ability to use voltammetry to evaluate the geometry of the electrode quickly.