Probing the Heterogeneous Ozonolysis of Squalene Nanoparticles by Photoemission

Jacobs, Michael I.; Xu, Bo; Kostko, Oleg; Heine, Nadja; Ahmed, Musahid; Wilson, Kevin R.

doi:10.1021/acs.jpca.6b09061

Title: Probing the Heterogeneous Ozonolysis of Squalene Nanoparticles by Photoemission

Journal Article · Mon Oct 17 00:00:00 EDT 2016 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.6b09061· OSTI ID:1377569

Jacobs, Michael I. ^[1]; Xu, Bo ^[2]; Kostko, Oleg ^[2]; Heine, Nadja ^[2]; Ahmed, Musahid ^[2]; Wilson, Kevin R. ^[2]

Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division

The heterogeneous reaction of ozone (O₃) with 200 nm squalene nanoparticles is studied in this paper using near-edge X-ray absorption fine structure (NEXAFS) and ultraviolet (UPS) and X-ray photoelectron spectroscopy (XPS). Photoelectrons are detected from free nanoparticle beams using a velocity map imaging (VMI) spectrometer capable of detecting photoelectrons with up to 40 eV of kinetic energy. Heterogeneous kinetics are quantified using changes in the UPS, XPS, and NEXAFS spectrum, yielding uptake coefficients for the decay of the double bonds in squalene of (3.1 ± 0.7) × 10^–4, (2.6 ± 0.6) × 10^–4, and (2.9 ± 0.7) × 10^–4, respectively. When comparing these values with the uptake coefficient, (1.0 ± 0.2) × 10^–3, determined by the molecular decay of squalene measured with aerosol mass spectrometry, it is found that on average 1.6 ± 0.2 double bonds are removed for each ozone-squalene reactive collision, suggesting the importance of evaporation of small molecular weight reaction products from the aerosol. From further analysis of the nanoparticle XPS spectrum, it is found that ozonolysis increases the oxygen-to-carbon (O:C) ratio of the aerosol to 0.43 ± 0.03 and produces 16 ± 4% and 84 ± 4% secondary ozonides and carbonyls, respectively. Finally, the methods developed here show how aerosol photoemission can be used to quantify heterogeneous reaction on free nanoparticles.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

DOE Contract Number:: AC02-05CH11231; DGE-1106400

OSTI ID:: 1377569

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 120, Issue 43; ISSN 1089-5639

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

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