Estudo teórico da adsorção de N2O e NO em superfícies nanogaiolas B12N12 puras e modificadas com metais de transição 3d

Abstract

Studies indicates that B12N12 nanocages can selectively detect gases such as O3, HNO, NO, CO, CNCl, and CNF, while metals modification extends detection to gases like CO, NH3, PH3, AsH3, SO2, O3, COCl2, NCCN, and CNCl. Studies demonstrate that B12N12 nanoclusters exhibit excellent adsorptive properties and electronic sensitivity, enabling applications in sensors, drug delivery, catalysis, and energy storage. The introduction of transition metals (TM) amplifies these properties. However, few studies have discussed the incorporation of different structural modifications in TM-modified nanocages, dynamic stability, optical properties, and the effects of interfering gases on nanocages. B12N12 was modified with first-row transition metals (TM = Sc - Zn) in five configurations (TMB11N12, B12N11TM, TM@b66, TM@b64, and TM@B12N12) and subjected to DFT calculations. Spin multiplicity analyses, cohesive energy, DOS, bond order, UV-vis, and DC were performed, along with molecular dynamics (DM) to assess the stability of nanocages. Some nanocages underwent rearrangement during geometry optimization or molecular dynamics. Modification of B12N12 reduced the HOMO-LUMO gap and increased reactivity of modified systems, with Zn being the only metal showing weak interaction. Cr@B12N12 stood out as the most stable system, exhibiting higher metal/cage affinity Regarding N2O gas, among all TM-B12N12 systems studied, Cu@B12N12 demonstrated higher sensitivity (∆Egap = 72.3 %) and the ability to selectively differentiate it from other gases, along with a better response in work function (∆Φ = 50.2 %). Subsequently, B12N12 modified with Cu was tested for NO gas adsorption, and Cu@B12N12 exhibited high electronic sensitivity

(ΔEgap = 87.4 %) and (∆Φ = 48.9 %) for selective NO gas detection. In summary, Cu- encapsulated systems emerge as promising sensor materials for selective detection of N2O, and

NO gases.