Modeling interfacial electric fields and the ethanol oxidation reaction at electrode surfaces

The electrochemical environment present at surfaces can have a large effect on intended applications. Such environments may occur, for instance, at battery or electrocatalyst surfaces. Solvent, co-adsorbates, and electrical field effects may strongly influence surface chemistry. Understanding these phenomena is an on-going area of research, especially in the realm of electrocatalysis. Herein, we modeled key steps in the ethanol oxidation reaction (EOR) over a common EOR catalyst, Rh(111), using density functional theory. We assessed how the presence of electrical fields may influence important C-C and C-H bond scission and C-O bond formation reactions with and without co-adsorbed water. We found that electric fields combined with the presence of water can significantly affect surface chemistry, including adsorption and reaction energies. Our results show that C-C scission (necessary for the complete oxidation of ethanol) is most likely through CHCO adsorbates. With no electric field or solvent present C-C scission of CHCO has the lowest reaction energy and dominates the oxidation of ethanol. But when applying strong negative fields (with or without solvent), the C-C scission of CH₂CO and CHCO becomes competitive. The current work provides insights into how electric fields and water solvent affect EOR, especially when simulated using density functional theory.