Nitrogen reduction reaction enhanced by single-atom transition metal catalysts on functionalized graphene: A first-principles study

Ammonia production seeks alternatives to the conventional Haber-Bosch process, with nitrogen reduction reaction (NRR) emerging promising. Addressing the challenge of efficient catalysts, the functionalized graphene-based single atom catalysts (SACs) stand out. While prior studies have favored heteroatom-doped catalysts, the coordination of metal centers with nitrogen atoms remains underexplored. This work investigates transition metal (TM) SACs on nitrogen-doped graphene (N3G) using density functional theory (DFT) for electro-catalytic NRR. Results highlight the stability of V@N3G, Mo@N3G, W@N3G, with binding energies of −7.77, −5.43, and −3.89 eV, respectively. Insights into work function, d-band center, N–N bond, and IR stretching's role in N2 activation are gained through this study. Bader charge analysis reveals electron redistribution between the support and adsorbed N2. Employing Computational Hydrogen Electrode (CHE) method, comparative free energy diagrams for TM@N3G (V, Mo, W) via., enzymatic, consecutive, alternating, and distal pathways outline potential rate determining step (PDS) with and without the Implicit solvation method. Remarkably, W@N3G catalyst exhibits the lowest PDS in the presence of solvation energy, surpassing other catalysts. The multi-adsorption of N2 on W@N3G enhances NRR process, stabilizing intermediates for efficient ammonia production. This computational study sheds light on metal center SACs on functionalized graphene support as a potential electro-catalyst for efficient and stable NRR.