Adsorption of Phosgene Gas on Pristine and Noble Metal-Doped B12N12 Nanocages: Insights from Density Functional Theory
Abstract
This study examines phosgene (COCl2) adsorption on pristine and noble metal-doped (Ag, Au, Pd, Pt) B12N12 nanocages using dispersion-corrected density functional theory [B3LYP-D3(BJ)]. Boron-site substitution narrows the HOMO-LUMO gap far more than nitrogen-site substitution (69-82% vs 41-67%) and was adopted throughout. All systems were fully optimized; multiple starting geometries converged to two stable minima per dopant, X-O and X-Cl. Pristine B12N12 binds phosgene weakly (Eads = -12.8 to -24.9 kJ mol^-1). Doping strengthens binding, spanning -14.0 to -60.7 kJ mol^-1 after counterpoise correction, with platinum exhibiting the highest affinity and structural stability. Natural population analysis indicates phosgene donates at most 0.33 e, and QTAIM classifies all cage-adsorbate bond critical points as closed-shell or intermediate, confirming physisorption. Vibrational frequency analysis confirms all structures as true minima and reveals that the adsorption entropy penalty (59-161 J mol^-1 K^-1) is decisive. Under Grimme's quasi-harmonic approximation, pristine cages fail to bind phosgene (Delta G = +23.8 to +27.9 kJ mol^-1), whereas only Pt-O (Delta G = -8.8 kJ mol^-1) and Pd-O (-7.2 kJ mol^-1) adsorb phosgene spontaneously at 298 K. Transition-state theory indicates rapid room-temperature recovery (tau = 43 ms for Pt-O), while thermodynamic desorption occurs at 69.6 deg C, ensuring a practical regeneration window. Silver-doped cages provide narrow post-adsorption gaps and high electrophilicity but cannot retain phosgene at ambient conditions. Platinum doping is therefore the most effective strategy for reversible phosgene detection using B12N12 nanocages.
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BibTeX
@misc{chowdhury2026adsorption,
title = {{Adsorption of Phosgene Gas on Pristine and Noble Metal-Doped B12N12 Nanocages: Insights from Density Functional Theory}},
author = {Shahariar Chowdhury and Mohammad Abdul Matin and Samiran Bhattacharjee and Ishtiaque M. Syed},
howpublished = {arXiv},
year = {2026},
month = sep,
doi = {10.48550/arxiv.2609.21678},
eprint = {2609.21678},
archivePrefix = {arXiv},
url = {https://arxiv.org/abs/2609.21678},
note = {CC BY 4.0},
}
RIS
TY - UNPB
TI - Adsorption of Phosgene Gas on Pristine and Noble Metal-Doped B12N12 Nanocages: Insights from Density Functional Theory
AU - Shahariar Chowdhury
AU - Mohammad Abdul Matin
AU - Samiran Bhattacharjee
AU - Ishtiaque M. Syed
PY - 2026
DA - 2026/09/18
PB - arXiv
DO - 10.48550/arxiv.2609.21678
UR - https://arxiv.org/abs/2609.21678
AB - This study examines phosgene (COCl2) adsorption on pristine and noble metal-doped (Ag, Au, Pd, Pt) B12N12 nanocages using dispersion-corrected density functional theory [B3LYP-D3(BJ)]. Boron-site substitution narrows the HOMO-LUMO gap far more than nitrogen-site substitution (69-82% vs 41-67%) and was adopted throughout. All systems were fully optimized; multiple starting geometries converged to two stable minima per dopant, X-O and X-Cl. Pristine B12N12 binds phosgene weakly (Eads = -12.8 to -24.9 kJ mol^-1). Doping strengthens binding, spanning -14.0 to -60.7 kJ mol^-1 after counterpoise correction, with platinum exhibiting the highest affinity and structural stability. Natural population analysis indicates phosgene donates at most 0.33 e, and QTAIM classifies all cage-adsorbate bond critical points as closed-shell or intermediate, confirming physisorption. Vibrational frequency analysis confirms all structures as true minima and reveals that the adsorption entropy penalty (59-161 J mol^-1 K^-1) is decisive. Under Grimme's quasi-harmonic approximation, pristine cages fail to bind phosgene (Delta G = +23.8 to +27.9 kJ mol^-1), whereas only Pt-O (Delta G = -8.8 kJ mol^-1) and Pd-O (-7.2 kJ mol^-1) adsorb phosgene spontaneously at 298 K. Transition-state theory indicates rapid room-temperature recovery (tau = 43 ms for Pt-O), while thermodynamic desorption occurs at 69.6 deg C, ensuring a practical regeneration window. Silver-doped cages provide narrow post-adsorption gaps and high electrophilicity but cannot retain phosgene at ambient conditions. Platinum doping is therefore the most effective strategy for reversible phosgene detection using B12N12 nanocages.
ER -