Carbon nanostructure and reactivity of soot particles from non-intrusive methods based on UV-VIS spectroscopy and time-resolved laser-induced incandescence
Fabian P. Hagen, Daniel Kretzler, Thomas Häber, H. Bockhorn, Rainer Suntz, Dimosthenis Trimis
Abstract
The objective of this study is to derive morphological and nanostructural properties of soot as well as the reactivity against low-temperature oxidation by O2 from easily measurable optical properties. First, ex-situ experiments utilizing thermogravimetric analysis (TGA) and high-resolution transmission electron microscopy (HRTEM) serve to evaluate the kinetics of soot oxidation with O2 and relate reactivity to particle morphology and nanostructure. Second, ultraviolet–visible (UV-VIS) absorption spectra provide wavelength-dependent absorption cross sections and refractive-index functions E(m~,λ). From these, optical band gap energies, EOG, and coefficients ξ∗ for single parameter functions describing the wavelength-dependency of E(m~,λ) are obtained. Third, from time-resolved laser-induced incandescence (TR-LII) ratios of the refractive-index functions E(m~,λi)/E(m~,λj) at three excitation wavelengths and primary particle size distributions are acquired. The ex-situ experiments show that the size of the graphene layers predominantly determines soot reactivity against oxidation. Graphene layer size and, therefore, soot reactivity are reflected in the UV-VIS absorption spectra and E(m~,λ), EOG, and ξ∗, respectively. Similarly, scattering-corrected ratios E(m~,λi)/E(m~,λj) from TR-LII also reflect graphene layer size and, hence, soot reactivity. The established strong correlations between the optical properties, nanostructural characteristics and reactivity against oxidation make UV-VIS spectroscopy as well as TR-LII useful fast in-situ diagnostic methods for soot reactivity.