Advanced Detection and Electrochemical Sensing of Hazardous Short-Branched Phthalate Plasticizers Using Novel Ga12N12 Nanomaterials: A DFT Study

Abstract

The semi-volatile chemicals phthalates are severely toxic and carcinogenic, causing adverse reproductive outcomes, allergy, asthma, diabetes II, obesity/overweight and dangerous effects on the hormonal system. These effects are unavoidable because of their wide applications in daily life personal care products, pharmaceutical products, cosmetics, paints, drugs, detergents, perfumes, and pesticides. For their detection, fullerene-like nanomaterials such as Ga₁₂N₁₂ can be used because of their adaptable characteristics and wide range of applications in electronics, optoelectronics, energy, and sensing technologies. They are essential for upcoming technological developments due to their distinctive wide bandgap, great thermal and chemical stability, and adjustable electrical and optical characteristics. Therefore, the utilization of Ga₁₂N₁₂ nanomaterial for phthalate detection and removal has not yet been thoroughly investigated. To fill this gap, the adsorption and the detection of short-branched phthalates including dimethyl phthalates, diethyl phthalates, methyl-ethyl phthalates, dipropyl phthalates and di-isobutyl phthalates (BP) have been explored through Ga₁₂N₁₂ nanomaterial employing benchmark DFT and TD-DFT calculations at B3LYP-D3/6-31G(d,p) functional. The computed adsorption energy values demonstrate the Ga₁₂N₁₂ nanomaterial’s exceptional adsorption response to each of the under-studied phthalates. The investigated molecule’s electronic characteristics include the hardness (~ 1.45 eV), energy gap (~ 2.90 eV), electrophilicity index(~ 6.70 eV), softness (~ 0.34 eV), electrical conductivity (~ 1.72 × 10⁹), and recovery time (~ 2.17 × 10⁻¹¹ s⁻¹) values ascertain an imperishable sensing response of the Ga₁₂N₁₂ nanomaterial. According to the UV–Vis analysis, all the studied complexes have increased electrical conductivity, a reduced band gap, maximal absorbance red-shifted to longer wavelengths, and enhanced sensor reactivity. NCI analysis explored that the studied Ga₁₂N₁₂ nanomaterial complexes indicated high-strength non-covalent interactions and correlated the information with the QTAIM results. Also, all the studied complexes indicate positive and higher Q_NBO values and the stronger transfer of charges from phthalates to the studied nanomaterial is associated with higher reactivity and maximum sensing response. The reaction mechanism was found to be spontaneous and strong, as indicated by the greater negative values of ∆_fH⁰ and ∆_rG⁰, as determined by thermodynamic analysis. Thus, all of the research parameters have demonstrated that the Ga₁₂N₁₂ nanomaterial is a highly effective and valuable sensor for the adsorption and identification of short-branched phthalates.

Graphical Abstract