Proceedings of MATSUS Fall 2023 Conference (MATSUSFall23)
DOI: https://doi.org/10.29363/nanoge.matsus.2023.089
Publication date: 18th July 2023
Alkali metal cation (AM+) is commonly used as counterions for anions in aqueous solutions due to its high solubility and ionic conductivity. This cation is typically situated near the electrode and constitute a key component of the electric double layer (EDL) structure, which is traditionally perceived as spectator species in electrochemical reactions. However, recent studies have shown the modulation of aqueous electrocatalysis depending on the identity and concentration of AM+. Several hypotheses have been proposed to explain the role of AM+ in electrocatalysis, while it is still under discussion. Here, we demonstrate that AM+s can directly participate on the model reaction of oxygen reduction reaction (ORR), forming chemical bonds with reactions intermediates and governing kinetics. This conclusion is corroborated by observing the NaO2 intermediate via advanced in situ spectroscopic analysis during the ORR on carbon surface. The Nernstian shift of polarization curve with varying AM+ concentrations and the significantly diminished ORR activity without free AM+, further demonstrate the pivotal role of AM+ in directly interacting with reaction intermediates in aqueous environments.
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