Axial Coordination Engineering on Fe−N−C Materials for Oxygen Reduction: Insights from Theory.

Autor: Mou, Yimin, Gao, Shurui, Wang, Yu, Li, Yafei
Předmět:
Zdroj: Chemistry - A European Journal; 12/10/2024, Vol. 30 Issue 69, p1-6, 6p
Abstrakt: Axial coordination engineering has emerged as an effective strategy to regulate the catalytic performance of metal−N−C materials for oxygen reduction reaction (ORR). However, the ORR mechanism and activity changes of their active centers modified by axial ligands are still unclear. Here, a comprehensive investigation of the ORR on a series of FeN4−L moieties (L stands for an axial ligand) is performed using advanced density functional theory (DFT) calculations. The axial ligand has a substantial effect on the electronic structure and catalytic activity of the FeN4 center. Specially, FeN4−C6H5 is screened as a promising active moiety with superior ORR activity, as further revealed by constant‐potential calculations and kinetic analysis. The enhanced activity is attributed to the weakened *OH adsorption caused by the altered electronic structure. Moreover, microkinetic modeling shows that at pH=1, FeN4−C6H5 possesses an impressive theoretical half‐wave potential of ~1.01 V, superior to the pristine Fe−N−C catalysts (~0.88 V) calculated at the same level. These findings advance the understanding of the ORR mechanism of FeN4−L and provide guidance for optimizing the ORR performance of single‐metal‐atom catalysts. [ABSTRACT FROM AUTHOR]
Databáze: Complementary Index