Elucidating the photodissociation fingerprint and quantifying the determination of organic hydroperoxides in gas-phase autoxidation

Hu, Zhihong; Di, Qimei; Liu, Bingzhi; Li, Yanbo; He, Yunrui; Zhu, Qingbo; Xu, Qiang; Dagaut, Philippe; Hansen, Nils; Sarathy, S. Mani; Xing, Lili; Truhlar, Donald G.; Wang, Zhandong

doi:10.1073/pnas.2220131120

Elucidating the photodissociation fingerprint and quantifying the determination of organic hydroperoxides in gas-phase autoxidation

Journal Article · Mon Feb 27 00:00:00 EST 2023 · Proceedings of the National Academy of Sciences of the United States of America

DOI:https://doi.org/10.1073/pnas.2220131120· OSTI ID:1958918

Hu, Zhihong ^[1]; Di, Qimei ^[1]; Liu, Bingzhi ^[1]; Li, Yanbo ^[1]; He, Yunrui ^[2]; Zhu, Qingbo ^[1]; ^[1]; ^[3]; Hansen, Nils ^[4]; ^[5]; Xing, Lili ^[2]; ^[6]; ^[7]

National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, Anhui 230029, P. R. China
Energy and Power Engineering Institute, Henan University of Science and Technology, Luoyang, Henan 471003, China
CNRS, Institut National des Sciences de l’Ingénierie et des Systèmes, Institut de Combustion, Aérothermique, Réactivité et Environnement, Orléans 45071, cedex 2, France
Combustion Research Facility, Sandia National Laboratories, Livermore, CA 94551
King Abdullah University of Science and Technology, Clean Combustion Research Center, Thuwal 23955-6900, Saudi Arabia
Department of Chemistry, Chemical Theory Center, and Minnesota Supercomputing Institute, University of Minnesota, Minneapolis, MN 55455-0431
National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, Anhui 230029, P. R. China, State Key Laboratory of Fire Science, University of Science and Technology of China, Hefei, Anhui 230026, P. R. China

Hydroperoxides are formed in the atmospheric oxidation of volatile organic compounds, in the combustion autoxidation of fuel, in the cold environment of the interstellar medium, and also in some catalytic reactions. They play crucial roles in the formation and aging of secondary organic aerosols and in fuel autoignition. However, the concentration of organic hydroperoxides is seldom measured, and typical estimates have large uncertainties. In this work, we developed a mild and environmental-friendly method for the synthesis of alkyl hydroperoxides (ROOH) with various structures, and we systematically measured the absolute photoionization cross-sections (PICSs) of the ROOHs using synchrotron vacuum ultraviolet-photoionization mass spectrometry (SVUV-PIMS). A chemical titration method was combined with an SVUV-PIMS measurement to obtain the PICS of 4-hydroperoxy-2-pentanone, a typical molecule for combustion and atmospheric autoxidation ketohydroperoxides (KHPs). We found that organic hydroperoxide cations are largely dissociated by loss of OOH. This fingerprint was used for the identification and accurate quantification of the organic peroxides, and it can therefore be used to improve models for autoxidation chemistry. The synthesis method and photoionization dataset for organic hydroperoxides are useful for studying the chemistry of hydroperoxides and the reaction kinetics of the hydroperoxy radicals and for developing and evaluating kinetic models for the atmospheric autoxidation and combustion autoxidation of the organic compounds.

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Research Organization:: Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Univ. of California, Oakland, CA (United States); Univ. of New Mexico, Albuquerque, NM (United States)

Sponsoring Organization:: Chinese Academy of Sciences (CAS); King Abdullah University of Science and Technology; National Key Research and Development Program of China; National Natural Science Foundation of China; USDOE; USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231; NA0003525; SC0015997

OSTI ID:: 1958918

Alternate ID(s):: OSTI ID: 2472300

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 Journal Issue: 10 Vol. 120; ISSN 0027-8424

Publisher:: Proceedings of the National Academy of SciencesCopyright Statement

Country of Publication:: United States

Language:: English

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Elucidating the photodissociation fingerprint and quantifying the determination of organic hydroperoxides in gas-phase autoxidation

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