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Issue 1, 2012
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Dynamic potential–pH diagrams application to electrocatalysts for wateroxidation

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The construction and use of “dynamic potential–pH diagrams” (DPPDs), that are intended to extend the usefulness of thermodynamic Pourbaix diagrams to include kinetic considerations is described. As an example, DPPDs are presented for the comparison of electrocatalysts for water oxidation, i.e., the oxygen evolution reaction (OER), an important electrochemical reaction because of its key role in energy conversion devices and biological systems (water electrolyses, photoelectrochemical water splitting, plant photosynthesis). The criteria for obtaining kinetic data are discussed and a 3-D diagram, which shows the heterogeneous electron transfer kinetics of an electrochemical system as a function of pH and applied potential is presented. DPPDs are given for four catalysts: IrO2, Co3O4, Co3O4 electrodeposited in a phosphate medium (CoPi) and Pt, allowing a direct comparison of the activity of different electrode materials over a broad range of experimental conditions (pH, potential, current density). In addition, the experimental setup and the factors affecting the accurate collection and presentation of data (e.g., reference electrode system, correction of ohmic drops, bubble formation) are discussed.

Graphical abstract: Dynamic potential–pH diagrams application to electrocatalysts for water oxidation

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The article was received on 29 Jul 2011, accepted on 01 Oct 2011 and first published on 03 Nov 2011

Article type: Edge Article
DOI: 10.1039/C1SC00516B
Chem. Sci., 2012,3, 217-229

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    Dynamic potential–pH diagrams application to electrocatalysts for water oxidation

    A. Minguzzi, F. F. Fan, A. Vertova, S. Rondinini and A. J. Bard, Chem. Sci., 2012, 3, 217
    DOI: 10.1039/C1SC00516B

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