Exploring Nitrogen Reduction Reaction Mechanisms with Graphyne-Confined Single-Atom Catalysts: A Computational Study Incorporating Electrode Potential and pH

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