Proceedings of MATSUS Fall 2023 Conference (MATSUSFall23)
DOI: https://doi.org/10.29363/nanoge.matsus.2023.147
Publication date: 18th July 2023
Hydrogen is an important energy vector and plays a key role in global plans to achieve net zero targets and low temperature water electrolysis is a viable technology to produce hydrogen at scale. The efficiency of water electrolysers, however, is limited by the sluggish kinetics of the oxygen evolution reaction (OER) at the anode, which contributes to a significant potential loss [1]. The search for new catalysts, has been largely focussed on optimising the binding energetics of the reaction intermediates on the surface by altering the materials chemistry. However, the role of the interfacial solvent on the OER kinetics is a largely unexplored lever to tune catalytic activity.
In this work, we investigate the influence of the nature of cations in the electrolyte on the OER kinetics on an iridium oxide catalyst in alkaline condition, in order to gain fundamental insight into the polarised solid-liquid interface. The activity in 0.1 M MOH (M = Li, Na, K, Cs) shows marked differences depending on the nature of the cation, with the OER activity being higher for larger cations. We performed operando uv-vis spectroscopy to quantify the potential-dependent redox transitions on the surface from 0.35 VRHE to 1.55 VRHE, and identify the binding energetics and the degree of interaction between surface adsorbates. In order to rationalise the trends in redox kinetics observed, laser-induced current transient measurements were employed to study the behavior of the interfacial water at the electrode surface. In particular, the potential of maximum entropy (PME) was determined for the different electrolyte compositions. This work provides a holistic picture of the electrified interface and allows us to determine how the nature of the electrolyte modulates the OER kinetics.
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