Formation and emission of large furans and oxygenated hydrocarbons from flames

Johansson, K. Olof; Dillstrom, Tyler; Monti, Matteo; El Gabaly, Farid; Campbell, Matthew F.; Schrader, Paul E.; Popolan-Vaida, Denisia M.; Richards-Henderson, Nicole K.; Wilson, Kevin R.; Violi, Angela; Michelsen, Hope A.

doi:10.1073/pnas.1604772113

Title: Formation and emission of large furans and oxygenated hydrocarbons from flames

Journal Article · Thu Jul 07 00:00:00 EDT 2016 · Proceedings of the National Academy of Sciences of the United States of America

DOI:https://doi.org/10.1073/pnas.1604772113· OSTI ID:1260993

Johansson, K. Olof; Dillstrom, Tyler; Monti, Matteo; El Gabaly, Farid; Campbell, Matthew F.; Schrader, Paul E.; Popolan-Vaida, Denisia M.; Richards-Henderson, Nicole K.; Wilson, Kevin R.; Violi, Angela; Michelsen, Hope A.

Many oxygenated hydrocarbon species formed during combustion, such as furans, are highly toxic and detrimental to human health and the environment. These species may also increase the hygroscopicity of soot and strongly influence the effects of soot on regional and global climate. However, large furans and associated oxygenated species have not previously been observed in flames, and their formation mechanism and interplay with polycyclic aromatic hydrocarbons (PAHs) are poorly understood. We report on a synergistic computational and experimental effort that elucidates the formation of oxygen-embedded compounds, such as furans and other oxygenated hydrocarbons, during the combustion of hydrocarbon fuels. We used ab initio and probabilistic computational techniques to identify low-barrier reaction mechanisms for the formation of large furans and other oxygenated hydrocarbons. We used vacuum-UV photoionization aerosol mass spectrometry and X-ray photoelectron spectroscopy to confirm these predictions. We show that fura ns are produced in the high- Temperature regions of hydrocarbon flames, where they remarkably survive and become the main functional group of oxygenates that incorporate into incipient soot. In controlled flame studies, we discovered ~100 oxygenated species previously unaccounted for. We found that large alcohols and enols act as precursors to furans, leading to incorporation of oxygen into the carbon skeletons of PAHs. Our results depart dramatically from the crude chemistry of carbonand oxygen-containing molecules previously considered in hydrocarbon formation and oxidation models and spearhead the emerging understanding of the oxidation chemistry that is critical, for example, to control emissions of toxic and carcinogenic combustion by-products, which also greatly affect global warming.

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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); USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC04-94AL85000; AC02-05CH11231; SC0002619

OSTI ID:: 1260993

Alternate ID(s):: OSTI ID: 1379529

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Vol. 113 Journal Issue: 30; ISSN 0027-8424

Publisher:: National Academy of Sciences, Washington, DC (United States)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 67 works

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
furans
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Title: Formation and emission of large furans and oxygenated hydrocarbons from flames

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