Comparing the Catalytic Effect of Metals for Energetic Materials: Machine Learning Prediction of Adsorption Energies on Metals.

Energetic materials (EMs) and metals are the important components of solid propellants, and a strong catalysis of metals on EMs could further enhance the combustion performance of solid propellants. Accordingly, the study on the adsorption of EMs such as octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), and ammonium dinitramide (ADN) on metals (Ti, Zr, Fe, Ni, Cu, and Al) was carried out by density functional theory (DFT) to reveal the catalytic effect of metals. The deep dissociation of EMs on Ti and Zr represents a stronger interaction and corresponds to the rapid thermal decomposition behavior of the EMs/metal composite in the experiment. It is expected that DFT calculation can be selected instead of experiments to compare the catalytic effect of metals and preliminarily screen out potential high-performance metals. Based on the data set of the calculated adsorption energy, further machine learning (ML) was used to predict the adsorption energy of EMs on metals for a convenient comparison of the catalytic effect of metals, since a quite high adsorption energy value represents a more thorough dissociation. The kernel ridge regression (KRR) method shows the best performance on predicting adsorption energy and helps to choose the metals for efficiently catalyzing ammonium nitrate (AN) and hexanitrohexaazaisowurtzitane (CL-20). Such adsorption computation and ML not only reveal the decomposition mechanism of EMs on metals but also provide a simple underlying method to predict the catalytic effect of metals.

Theoretical Kinetic Studies on Thermal Decomposition of Glycerol Trinitrate and Trimethylolethane Trinitrate in the Gas and Liquid Phases.

Glycerol trinitrate (NG) and trimethylolethane trinitrate (TMETN), as typical nitrate esters, are important energetic plasticizers in solid propellants. With the aid of high-precision quantum chemical calculations, the Rice-Ramsperger-Kassel-Marcus (RRKM)/master equation theory and the transition state theory have been employed to investigate the decomposition kinetics of NG and TMETN in the gas phase (over the temperature range of 300-1000 K and pressure range of 0.01-100 atm) and liquid phase (using water as the solvent). The continuum solvation model based on solute electron density (SMD) was used to describe the solvent effect. The thermal decomposition mechanism is closely relevant to the combustion properties of energetic materials. The results show that the RO-NO2 dissociation channel overwhelmingly favors other reaction pathways, including HONO elimination for the decomposition of NG and TMETN in both the gas phase and liquid phase. At 500 K and 1 atm, the rate coefficient of gas phase decomposition of TMETN is 5 times higher than that of NG. Nevertheless, the liquid phase decomposition of TMETN is a factor of 5835 slower than that of NG at 500 K. The solvation effect caused by vapor pressure and solubility can be used to justify such contradictions. Our calculations provide detailed mechanistic evidence for the initial kinetics of nitrate ester decomposition in both the gas phase and liquid phase, which is particularly valuable for understanding the multiphase decomposition behavior and building detailed kinetic models for nitrate ester.

Pb Single Atoms Enable Unprecedented Catalytic Behavior for the Combustion of Energetic Materials.

Manipulating the thermal decomposition behavior of energetic materials is the key to further pushing the combustion performance of solid rocket propellants. Herein, atomically dispersed Pb single atoms on polydopamine (PDA-Pb) are demonstrated, which display unprecedented catalytic activity toward the thermal decomposition of cyclotrimethylenetrinitramine (RDX). Impressively, RDX-based propellants with the addition of PDA-Pb catalyst exhibit substantially enhanced burning rates (14.98 mm s-1 at 2 MPa), which is 4.8 times faster than that without PDA-Pb and represents the best catalytic performance among Pb-based catalysts. Moreover, it also possesses low-pressure exponents in broad pressure ranges, which can enable more stable and safer combustion in solid rocket engines. Theoretical calculation unravels the efficient catalytic activity is stemmed from the enhanced interfacial electronic coupling between RDX and PDA-Pb via orbital level engineering. More importantly, PDA-Pb also presents similar catalytic behavior toward the decomposition of nitrocellulose, suggesting its broad catalytic generality. This work can open up new opportunities in the field of energetic compound combustion by exploring Pb-based single atom catalysts and beyond.

New theoretical insights into the reaction kinetics of toluene and hydroxyl radicals.

Toluene's removal mechanism in the atmosphere is mainly attributed to the OH radical, which includes major OH-addition and minor H-abstraction reactions. The cresols and RO2 derived from OH-adducts reacting with O2 have significant impacts on the generation of secondary organic aerosols (SOA) and O3. However, computed branching ratios of various OH-adducts at various theoretical levels are largely inconsistent, mainly because previously reported barrier heights of the OH-addition reaction showed a strong method dependence. In the present study, we demonstrate that this reaction involves a nonnegligible anharmonic effect (during the process of movement of OH to the benzene ring), which has been overlooked by previous studies. The reaction kinetics of toluene + OH was systematically studied by a high-level quantum chemical method (CCSD(T)-F12/cc-pVQZ-F12//B2PLYP-D3/6-311++G(d,p)) combined with RRKM/master equation simulations. The particle-in-a-box approximation was used to treat the anharmonicity in this system. The final total rate coefficient is calculated to be 3.02 × 10-12 cm3 molecule-1 s-1 at 300 K and 1 atm. The main products for toluene + OH are computed as ortho-adducts (69.8%), benzyl radical + H2O (11.9%), ipso-adduct (7.3%), para-adduct (5.1%), and meta-adduct (5.1%). Our results indicate that both high level quantum chemical calculations for the crucial barrier heights and appropriate treatments for the anharmonicity determine the accuracy of the final computed total rate coefficients and branching ratios. Further analysis of the branching ratios of various reaction channels provides insight into the atmosphere-initiated oxidation of toluene.