Density functional theory (DFT) simulations of the oxygen evolution reaction (OER) are considered essential for understanding the limitations of water splitting. Most DFT calculations of the OER use an acidic reaction mechanism and the standard hydrogen electrode (SHE) as reference electrode. However, experimental studies are usually carried out under alkaline conditions using the reversible hydrogen electrode (RHE) as reference electrode. The difference between the conditions in experiment and calculations is then usually taken into account by applying a pH-dependent correction factor to the latter. As, however, the OER reaction mechanisms under acidic and under alkaline conditions are quite different, it is not clear a priori whether a simple correction factor can account for this difference. We derive in this paper step by step the theory to simulate the OER based on the alkaline reaction mechanism and explain the OER process with this mechanism and the RHE as reference electrode. We compare the mechanisms for alkaline and acidic OER catalysis and highlight the roles of the RHE and the SHE. Our detailed analysis validates current OER simulations in the literature and explains the differences in OER calculations with acidic and alkaline mechanisms.
- Density functional theory (DFT)
- OER mechanism
- Oxygen evolution reaction (OER)