Abstract
To obtain more insight into the mechanisms of the decomposition of energetic compounds, we performed a computational study of the interaction of Fe13O13 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 Fe13O13). 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 Fe13O13. 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 Fe13O13 nanoparticles takes place along with a barrier-less electron transfer from Fe13O13 to TNT or NTO species.
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@article{Gorb2022,
title = {Decomposition of 2,4,6-trinitrotoluene (TNT) and 5-nitro-2,4- dihydro-3H-1,2,4-triazol-3-one (NTO) by Fe13O13 nanoparticle: density functional theory study},
author = {Leonid Gorb, Mykola Ilchenko, Jerzy Leszczynski},
doi = {10.1007/s11356-022-20547-w},
year = {2022},
date = {2022-05-11},
journal = {Environ. Sci. Pollut. Res.},
volume = {29},
pages = {68522\textendash68531},
abstract = {To obtain more insight into the mechanisms of the decomposition of energetic compounds, we performed a computational study of the interaction of Fe13O13 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 Fe13O13). 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 Fe13O13. 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 Fe13O13 nanoparticles takes place along with a barrier-less electron transfer from Fe13O13 to TNT or NTO species.},
note = {ARO grant W911NF-20-1-0116
},
keywords = {Decomposition, Density functional theory, Iron oxide, Nano-cluster, Nanoparticles, NTO, TNT},
pubstate = {published},
tppubtype = {article}
}