| Title: | Elucidating the photodissociation fingerprint and quantifying the determination of organic hydroperoxides in gas-phase autoxidation |
| Author(s): | Hu Z; Di Q; Liu B; Li Y; He Y; Zhu Q; Xu Q; Dagaut P; Hansen N; Sarathy SM; Xing L; Truhlar DG; Wang Z; |
| Address: | "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'Ingenierie et des Systemes, Institut de Combustion, Aerothermique, Reactivite et Environnement, Orleans 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. State Key Laboratory of Fire Science, University of Science and Technology of China, Hefei, Anhui 230026, P. R. China" |
| ISSN/ISBN: | 1091-6490 (Electronic) 0027-8424 (Print) 0027-8424 (Linking) |
| Abstract: | "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" |
| Keywords: | autoxidation ignition peroxy radicals photodissociation secondary organic aerosol; |
| Notes: | "PubMed-not-MEDLINEHu, 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 eng 2021YFA1601800/MOST | National Key Research and Development Program of China (NKPs)/ 51976208/National Natural Science Foundation of China (NSFC)/ 51906060/Ntuional natural science foundation of China/ 2020HSC-KPRD001/CAS | Hefei Science Center, Chinese Academy of Sciences (CAS Hefei Science Center)/ 2021HSC-UE006/CAS | Hefei Science Center, Chinese Academy of Sciences (CAS Hefei Science Center)/ DE-SC0015997/U.S. Department of Energy (DOE)/ 2023/02/28 Proc Natl Acad Sci U S A. 2023 Mar 7; 120(10):e2220131120. doi: 10.1073/pnas.2220131120. Epub 2023 Feb 27" |
