Advances in Selective Detection of Cadaverine by Electronic, Optical, and Work Function Sensors Based on Cu-Modified B12N12 and Al12N12 Nanocages: A Density Functional Theory (DFT) Study.

This work explores Cu-modified B₁₂N₁₂ and Al₁₂N₁₂ nanocages for cadaverine diamine (Cad) detection using advanced density functional theory (DFT) calculations. The study found that Cu modification altered the geometry of the nanocages, increased the dipole moment, reduced the energy gap, and enhanced the reactivity. While pristine B₁₂N₁₂ and Al₁₂N₁₂ were not sensitive to Cad, the modified Cu(b₆₄)B₁₂N₁₂ and Cu(b₆₆)Al₁₂N₁₂ nanocages showed significantly higher electronic sensitivity (Δgap = 39.8% and 35.6%, respectively), surpassing the literature data. However, molecular dynamics (MD) revealed that the Cu(b₆₆)Al₁₂N₁₂ nanocage is not stable in the long term, since the nanocage changes configuration to Cu(b₆₄)Al₁₂N₁₂, which is less sensitive and has an even longer recovery time for Cad sensing. Adsorption energy analysis (E_ads) showed a strong interaction of Cad/nanocages, while charge analysis suggested that the nanocages act as Lewis acids, accepting electrons from Cad. UV-vis spectra confirmed that Cu(b₆₄)B₁₂N₁₂ responds optically to the presence of Cad. Furthermore, Cu(b₆₄)B₁₂N₁₂ showed greater sensitivity to Cad compared to NO, H₂, H₂S, CO, COCl₂, N₂O, N₂ gases, or H₂O, showing high selectivity to diamine against interfering gases or water, standing out as a promising material for environmental applications in electronic, optical or work function sensors for cadaverine detection, even in humid environments.