Exploring Nitrogen\nReduction Reaction Mechanisms with\nGraphyne-Confined Single-Atom Catalysts: A Computational Study Incorporating\nElectrode Potential and pH

This\nstudy reconciles discrepancies between practical electrochemical\nconditions and theoretical density functional theory (DFT) frameworks,\nevaluating three graphyne-confined single-atom catalysts (Mo-TEB,\nMo@GY, and Mo@GDY). Using both constant charge models in vacuum and\nconstant potential models with continuum implicit solvation, we closely\nmimic real-world electrochemical environments. Our findings highlight\nthe crucial role of explicitly incorporating electrode potential and\npH in the constant potential model, providing enhanced insights into\nthe nitrogen reduction reaction (NRR) mechanisms. Notably, the superior\nNRR performance of Mo-TEB is attributed to the d-band center’s\nproximity to the Fermi level and enhanced magnetic moments at the\natomic center. This research advances our understanding of graphyne-confined\nsingle-atom catalysts as effective NRR platforms and underscores the\nsignificance of the constant potential model for accurate DFT studies\nof electrochemical reactions.