Abstract
To elucidate interfacial dynamics during electrocatalytic reactions, it is crucial to understand the adsorption behavior of organic molecules on catalytic electrodes within the electric double layer (EDL). However, the EDL structure in aqueous environments remains intricate when it comes to the electrochemical amination of acetone, using methylamine as a nitrogen source. Specifically, the interactions of acetone and methylamine with the copper electrode in water remain unclear, posing challenges in the prediction and optimization of reaction outcomes. In this study, initial investigations employed impedance spectroscopy at the potential of zero charge to explore the surface preconfiguration. Here, the capacitance of the EDL was utilized as a primary descriptor to analyze the adsorption tendencies of both acetone and methylamine. Acetone shows an increase in the EDL capacitance, while methylamine shows a decrease. Experiments are interpreted using combined grand canonical density functional theory and ab initio molecular dynamics to delve into the microscopic configurations, focusing on their capacitance and polarizability. Methylamine and acetone have larger molecular polarizability than water. Acetone shows a partial hydrophobic character due to the methyl groups, forming a distinct adlayer at the interface and increasing the polarizability of the liquid interface component. In contrast, methylamine interacts more strongly with water due to its ability to both donate and accept hydrogen bonds, leading to a more significant disruption of the hydrogen bond network. This disruption of the hydrogen network decreases the local polarizability of the interface and decreases the effective capacitance. Our findings underscore the pivotal role of EDL capacitance and polarizability in determining the local reaction environment, shedding light on the fundamental processes important for electro-catalysis.