High sensitivity of graphdiyne nanoflake toward detection of phosgene, thiophosgene and phosogenoxime; a first-principles study

• Published in: Journal of molecular graphics & modelling 2020-11, Vol.100, p.107658, Article 107658
• Main Authors: Khan, Sidra, Sajid, Hasnain, Ayub, Khurshid, Mahmood, Tariq
• Format: Article
• Language: English
• Subjects: DFT; Graphdiyne; Phosgene; Sensor
• ISSN: 1093-3263; 1873-4243
• DOI: 10.1016/j.jmgm.2020.107658

The sensing properties of 2D carbon materials are well explored for various gaseous analytes, however, the detection of toxic chemicals e.g., phosgene (Ph), thiophosgene (ThP) and phosogenoxime (PhO) are rarely studied. To the best of our literature survey, only a single study is found for the adsorption of phosgene on 2D carbon nanoflake (graphyne). This motivated us to explore the sensitivity of graphdiyne (GDY) nanoflake for the detection of phosgene and couple of its derivatives. Therefore, we have performed a density functional analysis to simulate the comparative interaction between phosgene, thiophosgene and phosogenoxime with graphdiyne nanoflake. The interaction behaviours are estimated by interaction energies, (symmetry adopted perturbation) SAPT0 analysis, (noncovalent interaction index) NCI analysis, molecular orbital analysis, natural bond orbital (NBO) charge transfer and UV–Vis absorption analysis. The obtained results demonstrate the trend in sensitivity of graphdiyne for analytes is PhO@GDY > ThP@GDY > Ph@GDY. The sensible justification for the particular observation is provided by the energy gaps between HOMO and LUMO orbitals in term of %sensitivity. The %sensitivity is in complete accord with the aforementioned trend. In addition, results suggest that graphdiyne based sensor for detecting phosgene and derivatives are better in sensitivity in comparison with already reported graphyne sensor. [Display omitted] •Adsorption of phosgene, thiophosgen and phosogenoxime molecules on graphdiyne nanoflake is studied.•ωB97XD/6-31+G (d,p) level of DFT has implied to elucidate the sensing applications.•Graphdiyne is highly sensitive toward phosgene and related derivatives.