Transition metals anchored on nitrogen-doped graphdiyne for an efficient oxygen reduction reaction: a DFT study

The search for highly active and low-cost single-atom catalysts for the oxygen reduction reaction (ORR) is essential for the widespread application of proton exchange membrane fuel cells. Transition metals anchored on nitrogen-doped graphdiyne (GDY) have attracted considerable interest as potentially excellent catalysts for the ORR. However, the relationship between the active site and nitrogen-doped GDY remains unclear. In this work, we conducted a systematic investigation of sp-hybridized N atoms anchoring single transition metal atoms of 3d and 4d on GDY (TMC₂N₂) as electrocatalysts for the ORR. Firstly, 18 kinds of TMC₂N₂ were determined to have good thermodynamic stability. Due to the extremely strong adsorption of *OH, TMC₂N₂ exhibits inferior ORR performance compared to traditional Pt(111). Considering that *OH adsorption hinders the catalytic activity of TMC₂N₂, we modified the OH ligand of TMC₂N₂ to develop the high-valent metal complex (TMC₂N₂-OH) aiming to enhance the electrocatalytic activity. The adsorption of intermediates on most TMC₂N₂-OH is weakened after the modification of the OH ligand, especially for the adsorption of *OH. Thus, by comparing the ORR overpotential of catalysts before and after ligand modification, we find that the catalytic activity of different TMC₂N₂-OHs improves to various degrees. MnC₂N₂-OH, TMC₂N₂-OH, and TcC₂N₂-OH exhibit relatively high ORR catalytic activity, with overpotentials of 0.93 V, 1.19 V, and 0.92 V, respectively. Furthermore, we investigated the cause of improved catalytic activity of TMC₂N₂-OH and found that the modified coordination environment of the catalyst led to adjusted adsorption of ORR intermediates. In summary, our work sheds light on the relationship between nitrogen-doped GDY and transition metal sites, thus contributing to the development of more efficient catalysts.