Boosting the Electrocatalytic Oxygen Reduction Activity of MnN 4 -Doped Graphene by Axial Halogen Ligand Modification.
Shaoqiang WeiRan ZhaoWenbo YuLei LiMin ZhangPublished in: Molecules (Basel, Switzerland) (2024)
Exploring highly active electrocatalysts as platinum (Pt) substitutes for the oxygen reduction reaction (ORR) remains a significant challenge. In this work, single Mn embedded nitrogen-doped graphene (MnN 4 ) with and without halogen ligands (F, Cl, Br, and I) modifying were systematically investigated by density functional theory (DFT) calculations. The calculated results indicated that these ligands can transform the d yz and d xz orbitals of Mn atom in MnN 4 near the Fermi-level into dz2 orbital, and shift the d -band center away from the Fermi-level to reduce the adsorption capacity for reaction intermediates, thus enhancing the ORR catalytic activity of MnN 4 . Notably, Br and I modified MnN 4 respectively with the lowest overpotentials of 0.41 and 0.39 V, possess superior ORR catalytic activity. This work is helpful for comprehensively understanding the ligand modification mechanism of single-atom catalysts and develops highly active ORR electrocatalysts.
Keyphrases
- density functional theory
- molecular dynamics
- metal organic framework
- room temperature
- electron transfer
- highly efficient
- transition metal
- carbon nanotubes
- molecular docking
- atomic force microscopy
- ionic liquid
- gold nanoparticles
- molecular dynamics simulations
- reduced graphene oxide
- single molecule
- crystal structure