The role of volatile organic compounds in the oxidation-driven fragmentation of soot particles

Abstract

In this work, the role of volatile organic compounds (VOCs) in soot oxidation and fragmentation was investigated in a lean, premixed CH4 flame. An aerosol generator was used to homogeneously disperse soot with and without VOCs (termed Soot-W and Soot-WO, respectively) into the flame. Because minimal soot was formed in the flame itself, information on the fragmentation of the Soot-W and Soot-WO during the oxidation process was readily captured to determine the role of VOCs in soot fragmentation. The integrated number concentration of fine mode particles and the degree of particle aggregation show that the presence of VOCs suppresses soot aggregate fragmentation, primarily by the mitigating consumption of the neck sites between primary particles due to the decreased specific surface area. The actual oxygen diffusion route and effective pore width between the crystallite structures were determined using the image analysis technique. To determine the characteristic regime of oxygen diffusion, the distribution of effective pore width was studied using high-resolution transmission electron microscopy and image analysis. The estimated effectiveness factor indicates that the presence of VOCs lowers the propensity of internal burning via intra-particle oxygen diffusion, and reduces the extent of primary particle fragmentation, as evidenced by a relatively smaller peak of ultrafine particles. The analysis of the nanostructure of neck sites vs. the bulk discovers significantly more disordered and thus reactive structure at neck sites, explaining the prevalence of aggregate fragmentation over primary particle fragmentation. The finding of the role of VOCs in oxidation-driven fragmentation is beneficial to the optimization of existing models for predicting the number concentration of fine and ultrafine particles. Furthermore, a better understanding of this role may aid in the control of the most harmful fine and ultrafine particle emissions.