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Updated: Sep 12, 2025

Synthesis of Metal Nanoparticles Supported on Carbon Nanotube with Doped Co and N Atoms and its Catalytic Applications in Hydrogen Production
Published on: December 6, 2021
Engineering graphyne-supported single-atom catalysts for efficient nitrogen reduction to ammonia: First-principles
Nahed H Teleb1, Yasmeen G Abou El-Reash2, Nuha Y Elamin2
1Electron Microscope and Thin Films Department, National Research Centre, El-Buhouth Str., Dokki, 12622, Giza, Egypt.
None:
The electrochemical nitrogen reduction reaction (N2RR) offers a sustainable route to ammonia production under ambient conditions but remains limited by inert N ≡ N bond activation and competitive hydrogen evolution reaction (HER). Herein, we employ first-principles density functional theory (DFT) to systematically investigate the N2RR activity of graphyne (GY) doped with single-atom transition metals (Fe, Mo, Ru, W). Structural analysis reveals strong binding and minimal distortion of the TM dopants on the porous, π-conjugated GY scaffold, with Fe-GY and W-GY exhibiting the highest stability. TM doping induces substantial bandgap narrowing and introduces localized d-orbital states near the Fermi level, enhancing charge transfer and catalytic potential. Adsorption studies show that TM sites effectively activate N2 via π-backdonation, with W-GY inducing the greatest N ≡ N bond elongation. Free energy profiles demonstrate that TM-GY catalysts significantly lower the limiting potential for N2RR compared to pristine GY, with Fe-Gy and W-GY achieving the most favorable limiting potential via the alternating mechanism. HER analysis reveals Ru-GY possesses near-optimal hydrogen adsorption energy (ΔGH = -0.25 eV), suggesting high activity but possible competition with N2RR. In contrast, Mo-GY and W-GY exhibit stronger H binding, potentially suppressing HER and improving N2RR selectivity. This work identifies TM-doped GY as a versatile platform for single-atom catalysis and offers design principles for optimizing selectivity and efficiency in electrochemical nitrogen fixation.
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