Probing the active sites of site-specific nitrogen doping in metal-free graphdiyne for electrochemical oxygen...

The development of highly active and low-cost catalysts for electrochemical reactions is one of the most attractive topics in the renewable energy technology. Herein, the site-specific nitrogen doping of graphdiyne (GDY) including grap-N, sp-N(I) and sp-N(II) GDY is systematically investigated as metal-free oxygen reduction electrocatalysts via density functional theory (DFT). Our results indicate that the doped nitrogen atom can significantly improve the oxygen (O₂) adsorption activity of GDY through activating its neighboring carbon atoms. The free-energy landscape is employed to describe the electrochemical oxygen reduction reaction (ORR) in both O₂ dissociation and association mechanisms. It is revealed that the association mechanism can provide higher ORR onset potential than dissociation mechanism on most of the substrates. Especially, sp-N(II) GDY exhibits the highest ORR electrocatalytic activity through increasing the theoretical onset potential to 0.76 V. This work provides an atomic-level insight for the electrochemical ORR mechanism on metal-free N-doped GDY.