▎ 摘　　要

There is too much controversy and too little interdisciplinary analysis of the role of carbon electrodes in a wide range of electrochemical and electrocatalytic processes. Here we focus on vanadium redox flow batteries (VRFB), which play a central role in the transition to renewable energy sources in the electricity sector of the global economy. We used density functional theory (DFT) to determine the relationship between chemically and electrocatalytically active sites on the positive electrode and the effects of chemical surface modification that introduces a variety of oxygen functional groups. Carefully selected aromatic (Ar) model clusters were analyzed to assess the extent of the electron density accumulation on and around the free carbon sites at graphene edges. The results reveal trends that help to resolve the controversies surrounding the role of phenolic or carboxyl groups in the redox mechanism. We conclude, in agreement with other chemical and electrocatalytic reactions that involve oxygen transfer (e.g., CO2 gasification or oxygen reduction reaction), that carbene-type edge carbon atoms are responsible for VO2+ adsorption and reduction of V5+ to V4+ in VO2+. The presence of Ar-OH and Ar-COOH groups can actually inhibit the redox process as a consequence of hydrogen and/or oxygen migration to the adjacent active sites. The presence of Ar=O groups, while affecting the electron density at the active sites, is confirmed to have a positive effect of stabilizing the free zigzag carbon sites in a triplet ground state.