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This work compared the surface functional group (SFG) types and concentrations and sp 3 /sp 2 hybridization ratios of in-cylinder soot samples generated by a heavy-duty diesel engine when employing n -heptane and a toluene/ n -heptane mixture (20% toluene by volume) as the fuels. In-cylinder soot samples were obtained from a total cylinder sampling system, and the SFGs and sp 3 /sp 2 hybridization ratios were analyzed using Fourier transform infrared and X-ray photoelectron spectroscopy. Despite the differences in fuel formulation, both n -heptane and n -heptane/toluene soot exhibited similar trends in terms of changes in the SFGs concentrations and sp 3 /sp 2 hybridization ratios during the combustion process. However, the addition of toluene to the n -heptane was found to increase the concentrations of all SFGs as well as the sp 3 /sp 2 hybridization ratio. The C OH and C O group concentrations exhibited a bimodal distribution for both the n -heptane and n -heptane/toluene soot throughout the combustion process, with the concentrations peaking in the premixed and diffusion combustion phases, respectively. In contrast, the relative amounts of aliphatic C H groups decreased in the premixed combustion phase, increased in the early diffusion combustion phase, and then decreased in the subsequent combustion phase. The sp 3 /sp 2 hybridization ratios obtained from both fuel soot were observed to initially decrease, then to increase before a decrease during the combustion process. There was a definite correlation between the sp 3 /sp 2 hybridization ratio and the relative concentration of aliphatic C H groups. [ABSTRACT FROM AUTHOR]

This work studied the evolution of in-cylinder polycyclic aromatic hydrocarbons (PAHs) in a diesel engine fueled with n -heptane, and explored the effects of adding toluene to n -heptane on in-cylinder PAHs. In-cylinder PAHs were sampled in a direct injection diesel engine using a total cylinder sampling system. PAHs were analyzed by gas chromatography–mass spectrometry with programmed temperature vaporization in the solvent vent mode. For n -heptane, the mass of total in-cylinder PAHs ( Σ M PAHs ) increased in premixed and late diffusion combustion phases, and decreased in early diffusion and late combustion phases. Among the 16 PAHs detected, Naphthalene (Nap) was the most abundant. PAHs with two benzene rings and one five-membered ring, such as Acenaphthylene, Acenaphthene and Fluorene, were also plentiful, implying that PAHs with five-membered ring could play an important role in the growth of in-cylinder PAHs. When adding 20 vol.% toluene to n -heptane, the evolution of ΣM PAHs was varied. The Σ M PAHs for n -heptane/toluene increased in premixed and early diffusion combustion phases, and decreased in late diffusion and late combustion phases. Toluene addition reduced the ΣM PAHs in the premixed combustion phase by up to 48% but increased ΣM PAHs by 30% in the early diffusion combustion phase. In the subsequent combustion phase, the ΣM PAHs was reduced by approximately 67%. For in-cylinder individual PAHs, toluene addition generally reduced the percentages of Nap in ΣM PAHs during the engine combustion process but increased the percentages of larger PAHs, indicating that toluene addition was conducive to the growth of PAHs to form larger PAHs. [ABSTRACT FROM AUTHOR]