Publication date: 28th August 2024
Overall, the oxygen evolution reaction, written 2 H2O --> O2 + 4 (H+ + e-), involves increasing the formal oxidation state of two oxygen atoms from minus two to zero. Along the way, the electrocatalyst facilitates this overall redox transition through redox movements of its own as metal-oxygen bonds are formed and broken. This interplay is defining both for the electrocatalytic activity but also for the stability of OER catalysts, which invariably metal oxides, as degradation also involves the breaking of metal-oxygen bonds. However, the formal oxidation state of the atoms is rarely communicated clearly in mechanistic proposals. Even if formal oxidation state is as much a bookkeeping method as a description of physical reality, we think that this bookkeeping contains important information, not least as a way of mapping out and comparing different OER mechanistic proposals. In this talk, proposed OER mechanisms will be analyzed according to formal oxidation states and formal movements of electrons and compared to each other on a universal map. The power of this approach will be demonstrated by examining previously proposed (and newly mapped) mechanisms for OER on iridium oxides in acidic electrolyte in the light of our latest in-situ experimental data.
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