Single Nanoparticle Mass Spectrometry as a High Temperature Kinetics Tool: Sublimation, Oxidation, and Emission Spectra of Hot Carbon Nanoparticles

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2015-12, Vol.119 (50), p.12538-12550
• Main Authors: Howder, Collin R, Long, Bryan A, Gerlich, Dieter, Alley, Rex N, Anderson, Scott L
• Format: Article
• Language: English
• Subjects: Carbon; Excitation; Mass spectrometry; Nanostructure; Oxidation; Reaction kinetics; Sublimation
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.5b08499

In single nanoparticle mass spectrometry, individual charged nanoparticles (NPs) are trapped in a quadrupole ion trap and detected optically, allowing their mass, charge, and optical properties to be monitored continuously. Previous experiments of this type probed NPs that were either fluorescent or large enough to detect by light scattering. Alternatively, small NPs can be heated to temperatures where thermally excited emission is strong enough to allow detection, and this approach should provide a new tool for measurements of sublimation and surface reaction kinetics of materials at high temperatures. As an initial test, we report a study of carbon NPs in the 20–50 nm range, heated by 10.6 μm, 532 nm, or 445 nm lasers. The kinetics for sublimation and oxidation of individual carbon NPs were studied, and a model is presented for the factors that control the NP temperature, including laser heating, and cooling by sublimation, buffer gas collisions, and radiation. The estimated NP temperatures were in the 1700–2000 K range, and the NP absorption cross sections ranged from ∼0.8 to 0.2% of the geometric cross sections for 532 nm and 10.6 μm excitation, respectively. Emission spectra of single NPs and small NP ensembles show a feature in the IR that appears to be the high energy tail of the thermal (blackbody-like) emission expected from hot particles but also a discrete feature peaking around 750 nm. Both the IR tail and 750 nm peak are observed for all particles and for both IR and visible laser excitation. No significant difference was observed between graphite and amorphous carbon NPs.