Journal Article

FZJ-2021-03817

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Cation Overcrowding Effect on the Oxygen Evolution Reaction

Huang, J. (Corresponding author)FZJ* ; Li, M. ; Eslamibidgoli, M. J.FZJ* ; Eikerling, M.FZJ* ; Groß, A.

2021
ACS Publications Washington, DC

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Please use a persistent id in citations: http://hdl.handle.net/2128/29548  doi:10.1021/jacsau.1c00315

Abstract: 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.

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Contributing Institute(s):

1. IEK-13 (IEK-13)
2. JARA-ENERGY (JARA-ENERGY)

Research Program(s):

1. 1231 - Electrochemistry for Hydrogen (POF4-123) (POF4-123)

Appears in the scientific report 2021

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Database coverage:
; ; ; ; Article Processing Charges ; Clarivate Analytics Master Journal List ; DOAJ Seal ; Emerging Sources Citation Index ; Fees ; IF >= 5 ; JCR ; PubMed Central ; SCOPUS ; Web of Science Core Collection

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