Cation Overcrowding Effect on the Oxygen Evolution Reaction
| Autor: | Axel Groß, Mengru Li, Mohammad Javad Eslamibidgoli, Michael Eikerling, Jun Huang |
|---|---|
| Jazyk: | angličtina |
| Rok vydání: | 2021 |
| Předmět: |
Oxygen evolution reaction
Electric double layer Oxygen evolution chemistry.chemical_element Thermodynamics Electrolyte Electrolyte cation effects Article Catalysis Nickel chemistry.chemical_compound Chemistry Adsorption chemistry ddc:540 Electrode Hydrogen production Local reaction condition Hydroxide Density functional theory QD1-999 Surface charging effects |
| Zdroj: | JACS Au, Vol 1, Iss 10, Pp 1752-1765 (2021) JACS Au JACS Au 1(10), 1752-1765 (2021). doi:10.1021/jacsau.1c00315 |
| ISSN: | 2691-3704 |
| DOI: | 10.1021/jacsau.1c00315 |
| Popis: | The influence of electrolyte ions on the catalytic activity of electrode/electrolyte interfaces is a controversial topic for many electrocatalytic reactions. Herein, we focus on an effect that is usually neglected, namely, how the local reaction conditions are shaped by nonspecifically adsorbed cations. We scrutinize the oxygen evolution reaction (OER) at nickel (oxy)hydroxide catalysts, using a physicochemical model that integrates density functional theory calculations, a microkinetic submodel, and a mean-field submodel of the electric double layer. The aptness of the model is verified by comparison with experiments. The robustness of model-based insights against uncertainties and variations in model parameters is examined, with a sensitivity analysis using Monto Carlo simulations. We interpret the decrease in OER activity with the increasing effective size of electrolyte cations as a consequence of cation overcrowding near the negatively charged electrode surface. The same reasoning could explain why the OER activity increases with solution pH on the RHE scale and why the OER activity decreases in the presence of bivalent cations. Overall, this work stresses the importance of correctly accounting for local reaction conditions in electrocatalytic reactions to obtain an accurate picture of factors that determine the electrode activity. |
| Databáze: | OpenAIRE |
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