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

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 (O) 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 O 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.