Role of ammonia addition on polycyclic aromatic hydrocarbon growth: A ReaxFF molecular dynamics study

Ammonia (NH3), one of the most promising carbon-free fuels, has received great research interest. In particular, NH3 is often blended with hydrocarbon fuels to achieve desired combustion characteristics. However, NH3 addition could affect soot formation, which has not been adequately understood. In this study, the effect of NH3 on the growth of polycyclic aromatic hydrocarbons (PAHs) is investigated with the reactive force field molecule dynamics (ReaxFF MD) simulations and quantum chemistry calculations. The simulation results indicate that NH3 addition slows down the growth of large carbon-containing species in the C2H4/O2 system. Novel path with HCN addition is discovered in the PAH growth, which inhibits the PAH growth compared to the conventional Hydrogen-Abstraction-Carbon-Addition (HACA) path via C2H2 addition. Moreover, quantum chemical calculations verified the rationality of this addition path and explained its inhibition on PAH growth by calculating the heat of reactions and reaction energy barriers. According to the present study, NH3 also has an inhibitory effect on both the HCN addition path and C2H2 addition path by providing H atoms to promote the generation of PAH radicals back to PAH molecules, and this effect is more significant for the C2H2 addition path. Results from the study provide a funda-mental insight for the inhibition of PAH growth due to the NH3 addition from an atomistic insight, which helps to improve the understanding of the combustion of blends of NH3 and hydrocarbon fuels.(c) 2023 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

Automated summary

In this study, the effect of NH3 on the growth of polycyclic aromatic hydrocarbons (PAHs) was investigated using simulations and quantum chemistry calculations. The results showed that NH3 addition slowed down the growth of large carbon-containing species in the C2H4/O2 system. A novel path with HCN addition was discovered, which inhibited PAH growth compared to the conventional Hydrogen-Abstraction-Carbon-Addition (HACA) path via C2H2 addition. The study provides fundamental insights into the inhibition of PAH growth due to NH3 addition.