Insights into heterogeneous atmospheric oxidation chemistry: Development of a tailor-made synthetic model for studying tropospheric surface chemistry

Andrea B. Voges, Grace Y. Stokes, Julianne M. Gibbs-Davis, Robert B. Lettan, Paul A. Bertin, Rachel C. Pike, Son Binh T. Nguyen, Karl A. Scheidt, Franz M. Geiger*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

48 Scopus citations

Abstract

The synthesis, characterization, and oxidation reaction of a tropospherically relevant terpene bound to a glass surface are reported. Vibrational broadband sum frequency generation (SFG) is used to characterize the various terpene-modified glass surfaces and track their interaction with ozone. SFG spectra indicate that, although orientations of the surface-bound terpenes depend on the linker strategies employed, the C=C double bond is accessible to gas-phase ozone regardless of the strategy applied. Exposure of the terpene-functionalized surface to ppm levels of ozone at 1 atm and 300 K yields an initial reaction probability of approximately 1 × 10-5 per surface collision, which is significantly higher than the corresponding gas-phase reaction involving 1-methyl-l-cyclohexene (5 × 10-7 from gas-phase collision theory). The interaction of ozone with a saturated octyl silane-functionalized glass surface leads to a slight molecular reorientation, or tilting, of the terminal CH3 groups on a much slower time scale. Our work demonstrates that SFG spectroscopy can be used to determine reaction probabilities of heterogeneous atmospheric reactions and bridges the gap between atmospheric chemistry and surface functionalization.

Original languageEnglish (US)
Pages (from-to)1567-1578
Number of pages12
JournalJournal of Physical Chemistry C
Volume111
Issue number4
DOIs
StatePublished - Feb 1 2007

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

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