Insights into local coordination environment of main group metal-nitrogen-carbon catalysts for enhanced oxygen reduction reaction

For the 4e – oxygen reduction reaction (ORR) on main group metal-nitrogen-carbon catalysts, the effect of the local coordination environment of main group metals on ORR has rarely been reported. By performing density functional theory (DFT) calculations, we screen 18 MN 4–x O x (x = 0–2, M = Mg, Ca, Sr, Al, Ga, In) candidates with different metal coordination environments and construct volcano curve between the adsorption free energy of OH* (ΔG OH* ) and ORR overpotential, yielding MgN 2 O 2 at the peak of the volcano with the overpotential as low as 0.55 V. The lower ORR overpotential on Mg coordinated with 2 N and 2 O atoms than other coordination environments is well explained by the decreased ΔG OH* because of more shifts of p-band position of Mg away from the Fermi energy level as well as the lower O highest occupied energy level when the number of the coordinated O atoms increases. Our DFT work provides theoretical guidance for engineering ORR performance of main group metal-nitrogen-carbon catalysts by modulating coordination environments.