Description

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The working electrode (WE) represents the most important component of an electrochemical cell. It is at the interface between the WE and the solution that electron transfers of greatest interest occur. The selection of a working electrode material is critical to experimental success. Several important factors should be considered. Firstly, the material should exhibit favorable redox behavior with the analyte, ideally fast, reproducible electron transfer without electrode fouling. Secondly, the potential window over which the electrode performs in a given electrolyte solution should be as wide as possible to allow for the greatest degree of analyte characterization. Additional considerations include the cost of the material, its ability to be machined or formed into useful geometries, the ease of surface renewal following a measurement, and toxicity.

The most commonly used working electrode materials are platinum, gold, carbon, and mercury. Among these, platinum is likely the favorite, demonstrating good electrochemical inertness and ease of fabrication into many forms. The biggest disadvantage to the use of platinum, other than its high cost, is that the presence of even small amounts of water or acid in the electrolyte leads to the reduction of hydrogen ion to form hydrogen gas (hydrogen evolution) at fairly modest negative potentials (E = -0.059 x pH). This reduction obscures any useful analytical signal.

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