Controlling HER activity and stability of $γ$- and 6,6,12-Graphyne through engineered B-N doping: DFT and Reactive MD simulations
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2026
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| author | Quispe, Juan Gomez Medina, Matheus Mishra, Subhendu Galvao, Douglas S Singh, Abhishek Autreto, Pedro Alves da Silva |
| author_facet | Quispe, Juan Gomez Medina, Matheus Mishra, Subhendu Galvao, Douglas S Singh, Abhishek Autreto, Pedro Alves da Silva |
| contents | Graphynes offer a chemically heterogeneous $sp/sp^{2}$ carbon framework with distinct electronic regimes and site-selective reactivity. Here, Density Functional Theory and Reactive Molecular Dynamics Simulations are combined to evaluate pristine, B-doped, N-doped, and B-N co-doped $γ$-graphyne and 6,6,12-graphyne (meta/ortho/para). $γ$-graphyne is a semiconductor, while 6,6,12-graphyne exhibits an anisotropic Dirac-like semi-metallic dispersion. B/N substitution reconstructs near-$E_F$ states via dopant $π$ hybridization, and B-N pairing stabilizes defects through donor-acceptor compensation, with the ortho substitutions being the most favorable. Hydrogen adsorption remains weak on pristine lattices but becomes locally optimized upon doping, with near thermo-neutral $ΔG_{\mathrm{ads}}$ 'hot spots' predominantly on $sp$-proximate carbon sites adjacent to the dopants. Reactive MD at 300 K further reveals an activity stability trade-off: B-N ortho in $γ$-graphyne sustains controlled hydrogen uptake without catastrophic bond scission, whereas B-N meta/para degrade, and 6,6,12-graphyne is generally more susceptible to over-hydrogenation. These results identify the B-N geometry as a key design variable for graphyne-based HER catalysts, which require both a favorable $ΔG_{\mathrm{ads}}$ and finite-temperature hydrogenation stability. |
| format | Preprint |
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arxiv_https___arxiv_org_abs_2601_15424 |
| institution | arXiv |
| publishDate | 2026 |
| record_format | arxiv |
| spellingShingle | Controlling HER activity and stability of $γ$- and 6,6,12-Graphyne through engineered B-N doping: DFT and Reactive MD simulations Quispe, Juan Gomez Medina, Matheus Mishra, Subhendu Galvao, Douglas S Singh, Abhishek Autreto, Pedro Alves da Silva Materials Science Other Condensed Matter Applied Physics Computational Physics Graphynes offer a chemically heterogeneous $sp/sp^{2}$ carbon framework with distinct electronic regimes and site-selective reactivity. Here, Density Functional Theory and Reactive Molecular Dynamics Simulations are combined to evaluate pristine, B-doped, N-doped, and B-N co-doped $γ$-graphyne and 6,6,12-graphyne (meta/ortho/para). $γ$-graphyne is a semiconductor, while 6,6,12-graphyne exhibits an anisotropic Dirac-like semi-metallic dispersion. B/N substitution reconstructs near-$E_F$ states via dopant $π$ hybridization, and B-N pairing stabilizes defects through donor-acceptor compensation, with the ortho substitutions being the most favorable. Hydrogen adsorption remains weak on pristine lattices but becomes locally optimized upon doping, with near thermo-neutral $ΔG_{\mathrm{ads}}$ 'hot spots' predominantly on $sp$-proximate carbon sites adjacent to the dopants. Reactive MD at 300 K further reveals an activity stability trade-off: B-N ortho in $γ$-graphyne sustains controlled hydrogen uptake without catastrophic bond scission, whereas B-N meta/para degrade, and 6,6,12-graphyne is generally more susceptible to over-hydrogenation. These results identify the B-N geometry as a key design variable for graphyne-based HER catalysts, which require both a favorable $ΔG_{\mathrm{ads}}$ and finite-temperature hydrogenation stability. |
| title | Controlling HER activity and stability of $γ$- and 6,6,12-Graphyne through engineered B-N doping: DFT and Reactive MD simulations |
| topic | Materials Science Other Condensed Matter Applied Physics Computational Physics |
| url | https://arxiv.org/abs/2601.15424 |