Interdisciplinary Center for Nanotoxicity, Department of Chemistry, Physics and Atmospheric Sciences, Jackson State University, P.O. Box 17910, 1325 Lynch Street, Jackson, MS, 39217, USA.
Department of Quantum and Molecular Biophysics Institute of Molecular Biology and Genetics, NAS of Ukraine, 150 Zabolotnogo, Kyiv, 03143, Ukraine.
Environ Sci Pollut Res Int. 2022 Sep;29(45):68522-68531. doi: 10.1007/s11356-022-20547-w. Epub 2022 May 11.
To obtain more insight into the mechanisms of the decomposition of energetic compounds, we performed a computational study of the interaction of FeO nanoparticles with two energetic molecules such as 2,4,6-trinitrotoluene (TNT) and 5-nitro-2,4-dihydro-3H-1,2,4-triazol-3-one (NTO). The density functional theory using M06-2X, B3LYP, and BLYP density functionals was applied. We found that the reactivity of these molecules strongly depends on the place of adsorption (so-called top and bottom planes of FeO). Namely, only the interaction with the bottom plane results in the thermodynamic characteristics of the decomposition that provide a medium reaction rate for the studied processes. Several pathways for such decomposition were found. One of them is the inter-complex oxygen transfer of nitro-group oxygen to FeO. This pathway results in the formation of adsorbed nitroso compounds. The second pathway describes a more complex decomposition that includes the transfer of the nitro-group oxygen accompanied by the hydrogen transfer. In all cases, the interaction of energetic molecules with FeO nanoparticles takes place along with a barrier-less electron transfer from FeO to TNT or NTO species.
为了更深入地了解含能化合物分解的机制，我们对 FeO 纳米粒子与两种含能分子（如 2,4,6-三硝基甲苯 (TNT) 和 5-硝基-2,4-二氢-3H-1,2,4-三唑-3-酮 (NTO)) 的相互作用进行了计算研究。我们应用了密度泛函理论中的 M06-2X、B3LYP 和 BLYP 密度泛函。我们发现这些分子的反应性强烈依赖于吸附位置（所谓的 FeO 的顶和底平面）。也就是说，只有与底平面的相互作用才能导致分解的热力学特性，为研究过程提供中等反应速率。我们发现了几种这样的分解途径。其中一种途径是硝酰基氧向 FeO 的间复合物氧转移。该途径导致吸附的亚硝基化合物的形成。第二种途径描述了一种更复杂的分解，包括硝酰基氧的转移伴随着氢的转移。在所有情况下，含能分子与 FeO 纳米粒子的相互作用都伴随着无势垒的电子从 FeO 向 TNT 或 NTO 物种的转移。
