Modulating Electronic Structures of Iron Clusters through Orbital Rehybridization by Adjacent Single Copper Sites for...

The atom-cluster interaction has recently been exploited as an effective way to increase the performance of metal-nitrogen-carbon catalysts for oxygen reduction reaction (ORR). However, the rational design of such catalysts and understanding their structure-property correlations remain a great challenge. Herein, we demonstrate that the introduction of adjacent metal (M)-N₄ single atoms (SAs) could significantly improve the ORR performance of a well-screened Fe atomic cluster (AC) catalyst by combining density functional theory (DFT) calculations and experimental analysis. The DFT studies suggest that the Cu-N₄ SAs act as a modulator to assist the O₂ adsorption and cleavage of O-O bond on the Fe AC active center, as well as optimize the release of OH* intermediates to accelerate the whole ORR kinetic. The depositing of Fe AC with Cu-N₄ SAs on nitrogen doped mesoporous carbon nanosheet are then constructed through a universal interfacial monomicelles assembly strategy. Consistent with theoretical predictions, the resultant catalyst exhibits an outstanding ORR performance with a half-wave potential of 0.92 eV in alkali and 0.80 eV in acid, as well as a high power density of 214.8 mW cm^-2 in zinc air battery. This work provides a novel strategy for precisely tuning the atomically dispersed poly-metallic centers for electrocatalysis.