Impact of hydrogenation on the structure, chemistry, and electrical properties of flame-synthesized carbon nanoparticle films

The interaction between hydrogen atoms and carbon nanoparticles is a fundamental process governing the properties of carbonaceous materials in environments ranging from combustion systems to the interstellar medium, and yet not fully understood. This study investigates the effects of controlled atomic hydrogen exposure on young and mature soot nanoparticles, generated in premixed ethylene-air flames, and deposited on substrates. We employed a multi-technique approach to characterize the chemical, mechanical, and electrical evolution of the films. In-situ infrared spectroscopy revealed non-monotonic behavior: an initial increase in aliphatic CH bonds was observed, followed by a decrease at higher hydrogen fluences, a trend more pronounced in the younger, more reactive soot film. This was accompanied by a continuous decrease in the aromatic C=C signal. Atomic force microscopy showed a significant increase in the Young's modulus of the film for both sample types after hydrogenation, indicating increased stiffness. This mechanical change was correlated with an increase in the I (D)/ I (G) ratio from Raman spectroscopy, suggesting structural modification. Furthermore, both macroscopic current vs. voltage and local scanning tunneling spectroscopy measurements demonstrated a notable increase in electrical conductivity. For single just-formed soot particles, moreover, a hydrogen-induced transformation from a semiconductive to a semi-metallic nature was observed, with the closing of the electronic band gap. The collective evidence points towards an H-induced CC cross-linking mechanism within the nanoparticle films. We propose that atomic hydrogen facilitates the formation of radical sites, which promotes covalent bond formation between adjacent particles or molecular units, creating a more interconnected and rigid network, with smaller interlayer distance. These findings provide crucial insights into the structural evolution of carbonaceous materials in hydrogen-rich environments, with direct implications for understanding soot formation and for the tailored design of carbon-based materials.