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.
|Original language||English (US)|
|Journal||Proceedings of the National Academy of Sciences|
|State||Published - Feb 27 2023|
Bibliographical noteKAUST Repository Item: Exported on 2023-03-02
Acknowledgements: We wish to thank Prof. Shanxi Tian, Prof. Linfan Zhu, Prof. Xiaoguo Zhou, Dr. Jiwen Guan, Dr. Tongpo Yu at the University of Science and Technology of China for valuable discussions, and Xiaobin Shan and Fuyi Liu for technical support. This work was supported by National Key Research and Development Program of China (2021YFA1601800); National Natural Science Foundation of China (51976208, 51906060); Chinese Academy of Sciences (CAS) Project for Young Scientists in Basic Research (YSBR-028); the Hefei Science Center, CAS (2020HSC-KPRD001, 2021HSC-UE005, 2021HSC-UE006); the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences (DE-SC0015997); and funding from King Abdullah University of Science and Technology. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC., a wholly owned subsidiary of Honeywell International, Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-NA0003525. The Advanced Light Source is supported by the Director, Office of Basic Energy Sciences, of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231.
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