Achieving Selective and Efficient Electrocatalytic Activity for CO₂ Reduction on N-Doped Graphene

The CO₂ electrochemical reduction reaction (CO₂RR) has been a promising conversion method for CO₂ utilization. Currently, the lack of electrocatalysts with favorable stability and high efficiency hindered the development of CO₂RR. Nitrogen-doped graphene nanocarbons have great promise in replacing metal catalysts for catalyzing CO₂RR. By using the density functional theory (DFT) method, the catalytic mechanism and activity of CO₂RR on 11 types of nitrogen-doped graphene have been explored. The free energy analysis reveals that the zigzag pyridinic N- and zigzag graphitic N-doped graphene possess outstanding catalytic activity and selectivity for HCOOH production with an energy barrier of 0.38 and 0.39 eV, respectively. CO is a competitive product since its free energy lies only about 0.20 eV above HCOOH. The minor product is CH₃OH and CH₄ for the zigzag pyridinic N-doped graphene and HCHO for zigzag graphitic N-doped graphene, respectively. However, for Z-pyN, CO₂RR is passivated by too strong HER. Meanwhile, by modifying the pH value of the electrolyte, Z-GN could be selected as a promising nonmetal electrocatalyst for CO₂RR in generating HCOOH.