Modelling gas adsorption onto Al12(Zn)N12 surfaces: A theoretical study of CH4, CO, CO2, H2O, N2, NH3, NO, NO2, O2, and SO2 interactions

• Published in: Computational and theoretical chemistry Vol. 1244; p. 115063
• Main Authors: Qadir, Karwan Wasman, Mohammadi, Mohsen Doust, Abdullah, Hewa Y.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01.02.2025
• Subjects: B12(Zn)O12; DFT; Intermolecular Interaction; NBO; QTAIM; B12(Zn)O12; NBO; DFT; Intermolecular Interaction; QTAIM
• ISSN: 2210-271X
• DOI: 10.1016/j.comptc.2024.115063

[Display omitted] •DFT computations unveil significant SO2 & NO2 adsorption affinities.•Bee colony optimization algorithm ensures optimal geometric arrangement.•CDFT analysis sheds light on SO2′s pronounced global reactivity.•NBO analysis elucidates notable charge transfer disparities.•QTAIM framework identifies robust van der Waals bonds. Utilizing Density Functional Theory (DFT) computations at the computational level ωB97XD/Def2tzvp, an in-depth analysis was conducted on the interaction of various gases including CH4, CO, CO2, H2O, N2, NH3, NO, NO2, O2, and SO2 with the Al12(Zn)N12 adsorbent. The investigation revealed a notable disparity in the affinity exhibited by SO2 and NO2 gases compared to the other gases. Specifically, SO2 and NO2 exhibited significantly higher adsorption energies, measured at 92.5 and 55.6 kcal/mol, respectively, under optimized conditions. To determine the optimal geometric arrangement of gas and adsorbent structures, a global optimization approach employing the bee colony algorithm was employed, ensuring attainment of the global minimum energy configuration. Conceptual DFT (CDFT) analysis provided crucial insights into the reactivity patterns of the chemical species involved, highlighting the pronounced global affinity of SO2. However, upon interaction with the Al12(Zn)N12 adsorbent, it was observed that SO2, despite its global affinity, did not exhibit the highest adsorption intensity. Further investigation using Natural Bond Orbital (NBO) analysis elucidated significant differences in charge transfer intensity between SO2 and NO2 gases compared to others, particularly in the presence of Al12(Zn)N12. Analysis of interatomic interactions through the Quantum Theory of Atoms in Molecules (QTAIM) framework revealed strong van der Waals interactions between SO2 and NO2 within the Al12(Zn)N12 domain, while interactions with other gases were predominantly non-covalent in nature. These findings underscore the sensitivity of the Al12(Zn)N12 adsorbent to various gases, providing valuable insights into its potential applications.