Abstract

Electrolyte engineering has recently been recognized as an integral component in the design of electrode/electrolyte interfaces for electrocatalysis. In particular, alkali metal cations of the supporting electrolyte are known to influence electrocatalytic processes. A better understanding of these cation effects requires methods capable of probing the distribution of alkali metal cations in the electrochemical double layer under reaction conditions. However, the scarcity of experimental technique capable of probing alkali metal cations greatly hinders further advances in leveraging cation effects in electrolyte engineering. In this talk, we will discuss our novel spectroscopic approach for quantifying the surface coverage of specifically adsorbed alkali metal cations, that is, the cations that are in direct contact with the electrode and therefore most likely to influence electrocatalysis. The technique is based on the use of an organic cation, tetramethylammonium (methyl4N+), as a vibrational probe of the electrode/electrolyte interface in the presence of alkali metal cations. We will discuss how we use this approach to characterize the adsorption of alkali metal cation during CO2-to-CO conversion.

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