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Modeling the Electrocatalytic Interface in the Conditions of Electrochemical Amination of Acetone with Methylamine as Nitrogen Source

Abstract

Electrochemical amination of acetone with methylamine as nitrogen source, the electric double layer on Cu electrode was studied in the conditions of electrochemical amination of acetone with methylamine as Nitrogen source. Therefore, double layer capacitance is used as a key descriptor to investigate the surface pre-configuration or preference of adsorption. It was found that in alkaline water solution, acetone (hydrophobic) and methylamine (hydrophilic) will result in different local dielectric property, which cause increase/decrease in Helmholtz capacitance.

Besides, it was observed that the working Cu electrode is corroded using mixtures of acetone and methylamine even under reductive potential conditions (-0.75V vs RHE). We employed Grand Canonical density functional theory to understand this dynamic process under potential from a microscopic perspective. We show that amine ligands in solution directly adsorb on the electrode, coordinate with the metal center, drive the rearrangement of the copper surface by extracting Cu atoms in low coordination positions, finally forming a detached Cu-tetramine di-cation complex in solution, even at negative potential conditions.

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