▎ 摘　　要

Understanding the mechanism of metal electrodeposition on graphene as the simplest building block of all graphitic materials is important for electrocatalysis and the creation of metal contacts in electronics. The present work investigates copper electrodeposition onto epitaxial graphene on 4H-SiC by experimental and computational techniques. The two subsequent single-electron transfer steps were coherently quantified by electrochemistry and density functional theory (DFT). The kinetic measurements revealed the instantaneous nucleation mechanism of copper (Cu) electrodeposition, controlled by the convergent diffusion of reactant to the limited number of nucleation sites. Cu can freely migrate across the electrode surface. These findings provide fundamental insights into the nature of copper reduction and nucleation mechanisms and can be used as a starting point for performing more sophisticated investigations and developing real applications.