Sensitivity of pure and Ni-decorated boron nitride B12N12 nanocages toward CH4, H2S, and N2 biogases: A DFT study

The sensitivity of pure and Ni-decorated boron nitride (B₁₂N₁₂) nanocages toward CH₄, H₂S, and N₂ biogases was adequately unveiled by employing versatile density functional theory (DFT) calculations. In this regard, the Gas∙∙∙B₁₂N₁₂ and ∙∙∙Ni@B₁₂N₁₂ complexes were studied within all possible configurations. Based on the energetic quantities, the Ni@B₁₂N₁₂ nanocage exhibited higher sensitivity than the pure one toward the investigated gases. Among all studied complexes, the H₂S∙∙∙Ni@B₁₂N₁₂ complex exhibited the most favorable adsorption (E_ads) and interaction (E_int) energies with values of –29.25 and –29.46 kcal/mol, respectively. According to the outlines of the quantum theory of atoms in molecules (QTAIM) and noncovalent interaction (NCI) index analyses, the closed-shell nature of the interactions within the investigated complexes was ensured. Substantial alterations in the molecular orbitals distribution patterns of pure and Ni-decorated B₁₂N₁₂ nanocages were observed, announcing the occurrence of the adsorption process within the investigated complexes. The obtained negative values of thermodynamic parameters ensured the spontaneous exothermic nature of the investigated Ni-decorated complexes. Upon density of states (DOS) analysis, the influence of adsorbed gases on the electronic characteristics of the pure and Ni-decorated B₁₂N₁₂ nanocages was highlighted. According to the emerging findings, the pure and Ni-decorated B₁₂N₁₂ nanocages are promising sensing materials for biogas components, especially CH₄, H₂S, and N₂ gases.