On the early stages of soot formation: molecular structure elucidation by high-resolution atomic force microscopy

Abstract The early stages of soot formation, namely inception and growth, are highly debated and central to many ongoing studies in combustion research. Here, we provide new insights into these processes from studying different soot samples by atomic force microscopy (AFM). Soot has been extracted from a slightly sooting, premixed ethylene/air flame both at the onset of the nucleation process, where the particle size is of the order of 2–4 nm, and at the initial stage of particle growth, where slightly larger particles are present. Subsequently, the molecular constituents from both stages of soot formation were investigated using high-resolution AFM with CO-functionalized tips. In addition, we studied a model compound to confirm the atomic contrast and AFM-based unambiguous identification of aliphatic pentagonal rings, which were frequently observed on the periphery of the aromatic soot molecules. We show that the removal of hydrogen from such moieties could be a pathway to resonantly stabilized π-radicals, which were detected in both investigated stages of the soot formation process. Such π-radicals could be highly important in particle nucleation, as they provide a rational explanation for the binding forces among aromatic molecules

Editorial: Experimental and modelling approaches for clean combustion technologies

Despite the rapid growth in alternative energy source utilization, combustion technologies will still play a major role in the years to come. Indeed, the energy mix of the next decades will see a coexistence of wind and solar sources and of combustion of e-fuels or synthetic fuels derived from renewable energies or produced from electricity excess, biofuels produced from non-edible biomass conversion (Dryer 2015; Elishav et al., 2020; Kohse-Höinghaus 2022), or unconventional sour fuels (Gupta et al., 2016)..

Particle inception in a Laminar premixed flame of benzene

Spectral optical techniques, including light extinction and laser induce fluorescence and incandescence measurements, are combined to characterize large-molecule soot precursors and soot in a slightly sooting flame of benzene at atmospheric pressure. Light absorption coupled to in-situ light scattering measurements and ex-situ Atomic Force Microscopy also allowed the evaluation of particle sizes. In the benzene flame high molecular mass structures with typical sizes of 3-4nm are formed in the main oxidation region of the flame. The radical-rich flame environment in which these compounds are formed promotes their dehydrogenation increasing the level of their aromaticity. As a result, nanoparticles with typical sizes of about 5nm, absorbing and fluorescing in the visible are formed. These compounds reach a maximum concentration just before the appearance of incandescent soot particles

Optical properties of incipient soot

The exact knowledge of the optical properties of soot nanoparticles is fundamental for several aspects including the correct determination of the soot concentration in combustion environments using optical diagnostics and the correct estimation of the environmental impact of the emitted particles. Although extensive researches over the years have led to a substantial agreement on the optical properties of mature soot particles, the optical properties of the incipient soot nanoparticles are still uncertain. From the particle inception point to the formation of large and more mature soot particles, the evolution of the optical properties must account for variations due to the size and the physicochemical transformation of the investigated particles. This work aims to determine the refractive index and optical properties of inception particles formed in lightly sooting flames. A previous determination based on in-situ light absorption and scattering measurements is revisited taking advantage of particle size measurements by differential mobility analysis. The spectral dependencies of the optical properties are derived by the Kramers-Krӧnig analysis of the ex-situ VUV-NIR light absorption measurements. Results confirm the strong decrease in the absorptivity in the vis-NIR region of inception particles with unimodal size distribution and d63∼3 nm, and confirm a strong size dependency of soot optical properties. The thermal-optical analysis of the sampled particles shows that the particle mass absorption coefficient also correlates with organic carbon content

Particle Inception in a Laminar Premixed Benzene Flame

Spectral optical techniques, including light extinction and laser induce fluorescence and incandescence measurements, are combined to characterize large-molecule soot precursors and soot in a slightly sooting flame of benzene at atmospheric pressure. Light absorption coupled to in-situ light scattering measurements and ex-situ Atomic Force Microscopy also allowed the evaluation of particle sizes. In the benzene flame high molecular mass structures with typical sizes of 3–4nm are formed in the main oxidation region of the flame. The radical-rich flame environment in which these compounds are formed promotes their dehydrogenation increasing the level of their aromaticity. As a result, nanoparticles with typical sizes of about 5 nm, absorbing and fluorescing in the visible are formed. These compounds reach a maximum concentration just before the appearance of incandescent soot particles