Adsorption and gas sensing performances of pristine and Ni-decorated fullerene/inorganic fullerene-like nanocages X12Y12 (X = Al, B and Y = N, P) nanocages toward CO and NO gases: DFT investigations

The detection and elimination of dangerous pollutants from the atmosphere are imminent due to environmental and human health hazards. The adsorption behaviors, selectivity, sensitivity, and conductivity of the pristine and decorated fullerene-like X₁₂Y₁₂ (C₂₄, B₁₂N₁₂, Al₁₂N₁₂, B₁₂P₁₂, and Al₁₂P₁₂) nanocages with Ni atom in sensing the hazardous CO and NO gases have been investigated through the density functional theory (DFT) and time-dependent density functional theory (TD-DFT) computations. Our results demonstrated that the Ni-doped fullerene-like X₁₂Y₁₂ exhibited a higher selectivity to CO and NO adsorption compared to pristine X₁₂Y₁₂ nanocages. The CO and NO are chemisorbed on Ni@C₂₄, Ni@B₁₂N₁₂, Ni@B₁₂P₁₂, and Ni@Al₁₂N₁₂ nanocages with high adsorption energies up to − 3.658 and − 3.823 eV, respectively. These nanocages are expected to be explored and developed for CO and NO elimination, capture, and sequestration. The reliability of the results was verified at both B3LYP/6-311G(d,p) and wB97XD/6-311G(d,p) functionals. Nevertheless, the CO and NO gases are only weakly chemisorbed on the Ni@Al₁₂P₁₂ with adsorption energies of − 0.838 eV and − 0.674 eV, respectively. The reduction in the energy gap of NO@Ni@Al₁₂P₁₂ is found to be − 35.300%, proving high sensitivity of the Ni@Al₁₂P₁₂ toward the NO gas molecule. High sensitivity and rapid recovery time (97.136 s and 0.178 s) affirmed the potency of Ni@Al₁₂P₁₂ nanocage as a promising sensing material for CO and NO gas molecules. The desorption of CO and NO gas molecules from Ni@B₁₂P₁₂ takes place within a reasonable time of 2.403 s and 1.750 s at a temperature of 800 K, respectively. As a result, the Ni@B₁₂P₁₂ nanocage may achieve potential applications for sensing CO and NO gases from vehicle exhaust and factory emissions. Thermodynamic parameters demonstrated the spontaneous exothermic nature of Ni@X₁₂Y₁₂ nanocages before and after the adsorption of CO and NO gases. New energy states were visualized through the spin-polarized partial density of states (PDOS) analysis, indicating the effect of adsorbing CO and NO molecules on the electronic characteristics of the Ni@X₁₂Y₁₂ nanocages. More precisely, the CO and NO adsorption behavior at Ni@X₁₂Y₁₂ is well correlated with the molecular electrostatic potential (MESP), recovery times, quantum theory of atoms in molecules (QTAIM), and non-covalent interaction index (NCI). The presence of further peaks in the infrared spectra demonstrated the apparent impact of the adsorption process on the characteristics of the Ni@X₁₂Y₁₂ nanocages. Based on UV–Vis spectra and the most significant values of first hyperpolarizability β_o, the NO@Ni@Al₁₂P₁₂ system is the most promising candidate for optical and photonic applications. These results may help provide a reliable platform for further experimental investigations of Ni@X₁₂Y₁₂ nanostructured materials.