Soot particle morphology and polycyclic aromatic hydrocarbons formation molecular dynamics during diffusion...

Soot particles constitute a major pollutant in engine diffusion combustion, posing a serious threat to human health and the atmospheric environment. The employment of carbon-neutral biofuel, pentanol, in engines contributes to reducing soot emissions; however, its effectiveness is contingent upon the position of the OH functional group. This work investigated the soot morphology and microstructural parameters evolution of three pentanol isomers, and explored the influence mechanism of OH functional group positional isomerism on the entire process of PAHs formation at the atomic level. The results showed that the peak of primary particle size and soot volume fraction in pentanol flames showed a trend of 2-pentanol>3-pentanol>1-pentanol, and the initial formation time of soot in 1-pentanol flame is the latest, and the particle aggregate size is the smallest. The entire process of pentanol isomers soot formation can be divided into four stages: fuel pyrolysis forming initial ring, PAHs growing into initial soot, soot chain growth and structural evolution, soot morphology transformation and maturation. Among the three isomers, 2-pentanol has the fastest initial ring formation rate, the highest peak C-number in the largest molecule, and ultimately forms a more mature fullerene-like structure. 1-pentanol has the slowest initial ring formation rate, the lowest peak C-number in the largest molecule, ultimately forms a lower maturity layered structure. In terms of reaction pathways, H-atom abstraction and dehydroxylation reactions jointly dominate the initial decomposition pathway in 1-pentanol combustion, while in 2-pentanol, dehydroxylation becomes the main initial decomposition pathway due to the high stability of H atoms on β‑carbon. The dehydroxylation reaction tends to generate olefins, promoting the generation of C1-C4 hydrocarbon. The oxygen atom bonded on the α‑carbon site exhibits a stronger carbon fixation ability, and C1-C4 hydrocarbons are more inclined to participate in oxidation to form CO rather than promote the soot production.