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 · Sun Feb 26 23:00:00 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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Sponsoring Organization:: USDOE

Grant/Contract Number:: 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

References (54)

Experimental Confirmation of the Low-Temperature Oxidation Scheme of Alkanes Battin-Leclerc, Frédérique; Herbinet, Olivier; Glaude, Pierre-Alexandre Angewandte Chemie International Edition, Vol. 49, Issue 18 https://doi.org/10.1002/anie.200906850	journal	April 2010
Rapid Autoxidation Forms Highly Oxidized RO ₂ Radicals in the Atmosphere Jokinen, Tuija; Sipilä, Mikko; Richters, Stefanie Angewandte Chemie International Edition, Vol. 53, Issue 52 https://doi.org/10.1002/anie.201408566	journal	October 2014
Formation of Organic Acids and Carbonyl Compounds in n ‐Butane Oxidation via γ‐Ketohydroperoxide Decomposition Popolan‐Vaida, Denisia M.; Eskola, Arkke J.; Rotavera, Brandon Angewandte Chemie International Edition, Vol. 61, Issue 42 https://doi.org/10.1002/anie.202209168	journal	September 2022
Determination of absolute photoionization cross-sections of aromatics and aromatic derivatives Zhou, Zhongyue; Xie, Mingfeng; Wang, Zhandong Rapid Communications in Mass Spectrometry, Vol. 23, Issue 24 https://doi.org/10.1002/rcm.4339	journal	December 2009
The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals Zhao, Yan; Truhlar, Donald G. Theoretical Chemistry Accounts, Vol. 120, Issue 1-3 https://doi.org/10.1007/s00214-007-0310-x	journal	July 2007
Chemical aspects of the autoignition of hydrocarbonair mixtures Cox, R. A.; Cole, J. A. Combustion and Flame, Vol. 60, Issue 2 https://doi.org/10.1016/0010-2180(85)90001-X	journal	May 1985
A comparative risk assessment of burden of disease and injury attributable to 67 risk factors and risk factor clusters in 21 regions, 1990–2010: a systematic analysis for the Global Burden of Disease Study 2010 Lim, Stephen S.; Vos, Theo; Flaxman, Abraham D. The Lancet, Vol. 380, Issue 9859 https://doi.org/10.1016/S0140-6736(12)61766-8	journal	December 2012
Cool flame chemistry of diesel surrogate compounds: n-Decane, 2-methylnonane, 2,7-dimethyloctane, and n-butylcyclohexane Wang, Zhandong; Hansen, Nils; Jasper, Ahren W. Combustion and Flame, Vol. 219 https://doi.org/10.1016/j.combustflame.2020.06.003	journal	September 2020
Experimental characterization of n-heptane low-temperature oxidation products including keto-hydroperoxides and highly oxygenated organic molecules (HOMs) Belhadj, Nesrine; Benoit, Roland; Dagaut, Philippe Combustion and Flame, Vol. 224 https://doi.org/10.1016/j.combustflame.2020.10.021	journal	February 2021
Understanding the antagonistic effect of methanol as a component in surrogate fuel models: A case study of methanol/n-heptane mixtures Wu, Yingtao; Panigrahy, Snehasish; Sahu, Amrit B. Combustion and Flame, Vol. 226 https://doi.org/10.1016/j.combustflame.2020.12.006	journal	April 2021
Experimental and kinetic modeling study of n-pentane oxidation at 10 atm, Detection of complex low-temperature products by Q-Exactive Orbitrap Belhadj, Nesrine; Lailliau, Maxence; Benoit, Roland Combustion and Flame, Vol. 235 https://doi.org/10.1016/j.combustflame.2021.111723	journal	January 2022
Improving quantification of hydrogen peroxide by synchrotron vacuum ultraviolet photoionization mass spectrometry Dong, Bin; Hu, Zhihong; Xu, Qiang Combustion and Flame, Vol. 242 https://doi.org/10.1016/j.combustflame.2022.112214	journal	August 2022
Recent contributions of flame-sampling molecular-beam mass spectrometry to a fundamental understanding of combustion chemistry Hansen, Nils; Cool, Terrill A.; Westmoreland, Phillip R. Progress in Energy and Combustion Science, Vol. 35, Issue 2 https://doi.org/10.1016/j.pecs.2008.10.001	journal	April 2009
Exploring hydroperoxides in combustion: History, recent advances and perspectives Wang, Zhandong; Herbinet, Olivier; Hansen, Nils Progress in Energy and Combustion Science, Vol. 73 https://doi.org/10.1016/j.pecs.2019.02.003	journal	July 2019
Combustion chemistry probed by synchrotron VUV photoionization mass spectrometry Qi, Fei Proceedings of the Combustion Institute, Vol. 34, Issue 1 https://doi.org/10.1016/j.proci.2012.09.002	journal	January 2013
Probing the low-temperature chain-branching mechanism of n -butane autoignition chemistry via time-resolved measurements of ketohydroperoxide formation in photolytically initiated n- C 4 H 10 oxidation Eskola, A. J.; Welz, O.; Zádor, J. Proceedings of the Combustion Institute, Vol. 35, Issue 1 https://doi.org/10.1016/j.proci.2014.05.011	journal	January 2015
Measuring hydroperoxide chain-branching agents during n-pentane low-temperature oxidation Rodriguez, Anne; Herbinet, Olivier; Wang, Zhandong Proceedings of the Combustion Institute, Vol. 36, Issue 1 https://doi.org/10.1016/j.proci.2016.05.044	journal	January 2017
An experimental and kinetic modeling study of the auto-ignition of natural gas blends containing C1–C7 alkanes El-Sabor Mohamed, A. Abd; Panigrahy, Snehasish; Sahu, Amrit Bikram Proceedings of the Combustion Institute, Vol. 38, Issue 1 https://doi.org/10.1016/j.proci.2020.06.015	journal	January 2021
Highly Oxygenated Organic Molecules (HOM) from Gas-Phase Autoxidation Involving Peroxy Radicals: A Key Contributor to Atmospheric Aerosol Bianchi, Federico; Kurtén, Theo; Riva, Matthieu Chemical Reviews, Vol. 119, Issue 6 https://doi.org/10.1021/acs.chemrev.8b00395	journal	January 2019
Detection and Identification of the Keto-Hydroperoxide (HOOCH ₂ OCHO) and Other Intermediates during Low-Temperature Oxidation of Dimethyl Ether Moshammer, Kai; Jasper, Ahren W.; Popolan-Vaida, Denisia M. The Journal of Physical Chemistry A, Vol. 119, Issue 28 https://doi.org/10.1021/acs.jpca.5b00101	journal	February 2015
Quantification of the Keto-Hydroperoxide (HOOCH ₂ OCHO) and Other Elusive Intermediates during Low-Temperature Oxidation of Dimethyl Ether Moshammer, Kai; Jasper, Ahren W.; Popolan-Vaida, Denisia M. The Journal of Physical Chemistry A, Vol. 120, Issue 40 https://doi.org/10.1021/acs.jpca.6b06634	journal	September 2016
Hydroperoxide Measurements During Low-Temperature Gas-Phase Oxidation of n- Heptane and n- Decane Rodriguez, Anne; Herbinet, Olivier; Meng, Xiangzan The Journal of Physical Chemistry A, Vol. 121, Issue 9 https://doi.org/10.1021/acs.jpca.6b10378	journal	February 2017
Exploitation of Synchrotron Radiation Photoionization Mass Spectrometry in the Analysis of Complex Organics in Interstellar Model Ices Zhu, Cheng; Wang, Hailing; Medvedkov, Iakov The Journal of Physical Chemistry Letters, Vol. 13, Issue 30 https://doi.org/10.1021/acs.jpclett.2c01628	journal	July 2022
Quantification of Hydrogen Peroxide during the Low-Temperature Oxidation of Alkanes Bahrini, Chiheb; Herbinet, Olivier; Glaude, Pierre-Alexandre Journal of the American Chemical Society, Vol. 134, Issue 29 https://doi.org/10.1021/ja305200h	journal	July 2012
The Formation of Highly Oxidized Multifunctional Products in the Ozonolysis of Cyclohexene Rissanen, Matti P.; Kurtén, Theo; Sipilä, Mikko Journal of the American Chemical Society, Vol. 136, Issue 44 https://doi.org/10.1021/ja507146s	journal	October 2014
Quantitative Measurements of HO ₂ and Other Products of n -Butane Oxidation (H ₂ O ₂ , H ₂ O, CH ₂ O, and C ₂ H ₄ ) at Elevated Temperatures by Direct Coupling of a Jet-Stirred Reactor with Sampling Nozzle and Cavity Ring-Down Spectroscopy (cw-CRDS) Djehiche, Mokhtar; Le Tan, Ngoc Linh; Jain, Chaithanya D. Journal of the American Chemical Society, Vol. 136, Issue 47 https://doi.org/10.1021/ja510719k	journal	November 2014
Lowering of Reaction Rates by Energetically Favorable Hydrogen Bonding in the Transition State. Degradation of Biofuel Ketohydroperoxides by OH Xing, Lili; Lian, Liuchao; Wang, Zhandong Journal of the American Chemical Society, Vol. 144, Issue 37 https://doi.org/10.1021/jacs.2c06124	journal	September 2022
Degradation of Carbonyl Hydroperoxides in the Atmosphere and in Combustion Xing, Lili; Bao, Junwei Lucas; Wang, Zhandong Journal of the American Chemical Society, Vol. 139, Issue 44 https://doi.org/10.1021/jacs.7b08297	journal	October 2017
Autoxidation of Organic Compounds in the Atmosphere Crounse, John D.; Nielsen, Lasse B.; Jørgensen, Solvejg The Journal of Physical Chemistry Letters, Vol. 4, Issue 20 https://doi.org/10.1021/jz4019207	journal	September 2013
A large source of low-volatility secondary organic aerosol Ehn, Mikael; Thornton, Joel A.; Kleist, Einhard Nature, Vol. 506, Issue 7489 https://doi.org/10.1038/nature13032	journal	February 2014
Mild oxidation of methane to methanol or acetic acid on supported isolated rhodium catalysts Shan, Junjun; Li, Mengwei; Allard, Lawrence F. Nature, Vol. 551, Issue 7682 https://doi.org/10.1038/nature24640	journal	November 2017
Hydroxyl radical-induced formation of highly oxidized organic compounds Berndt, Torsten; Richters, Stefanie; Jokinen, Tuija Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms13677	journal	December 2016
Low-temperature formation of polycyclic aromatic hydrocarbons in Titan’s atmosphere Zhao, Long; Kaiser, Ralf I.; Xu, Bo Nature Astronomy, Vol. 2, Issue 12 https://doi.org/10.1038/s41550-018-0585-y	journal	October 2018
Au-ZSM-5 catalyses the selective oxidation of CH4 to CH3OH and CH3COOH using O2 Qi, Guodong; Davies, Thomas E.; Nasrallah, Ali Nature Catalysis, Vol. 5, Issue 1 https://doi.org/10.1038/s41929-021-00725-8	journal	January 2022
Elucidation of radical- and oxygenate-driven paths in zeolite-catalysed conversion of methanol and methyl chloride to hydrocarbons Cesarini, Alessia; Mitchell, Sharon; Zichittella, Guido Nature Catalysis, Vol. 5, Issue 7 https://doi.org/10.1038/s41929-022-00808-0	journal	June 2022
Efficient alkane oxidation under combustion engine and atmospheric conditions Wang, Zhandong; Ehn, Mikael; Rissanen, Matti P. Communications Chemistry, Vol. 4, Issue 1 https://doi.org/10.1038/s42004-020-00445-3	journal	February 2021
Intramolecular CH₃-migration-controlled cation reactions in the VUV photochemistry of 2-methyl-3-buten-2-ol investigated by synchrotron photoionization mass spectrometry and theoretical calculations Li, Yanbo; Chen, Weiye; Zhu, Long Physical Chemistry Chemical Physics, Vol. 23, Issue 17 https://doi.org/10.1039/D1CP00490E	journal	January 2021
Gaussian-4 theory Curtiss, Larry A.; Redfern, Paul C.; Raghavachari, Krishnan The Journal of Chemical Physics, Vol. 126, Issue 8 https://doi.org/10.1063/1.2436888	journal	February 2007
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen Dunning, Thom H. The Journal of Chemical Physics, Vol. 90, Issue 2 https://doi.org/10.1063/1.456153	journal	January 1989
Evaluated Kinetic Data for Combustion Modelling Baulch, D. L.; Cobos, C. J.; Cox, R. A. Journal of Physical and Chemical Reference Data, Vol. 21, Issue 3 https://doi.org/10.1063/1.555908	journal	May 1992
Ionization energies and cationic bond dissociation energies of RuB, RhB, OsB, IrB, and PtB Merriles, Dakota M.; Morse, Michael D. The Journal of Chemical Physics, Vol. 157, Issue 7 https://doi.org/10.1063/5.0107086	journal	August 2022
Production of extremely low volatile organic compounds from biogenic emissions: Measured yields and atmospheric implications Jokinen, Tuija; Berndt, Torsten; Makkonen, Risto Proceedings of the National Academy of Sciences, Vol. 112, Issue 23 https://doi.org/10.1073/pnas.1423977112	journal	May 2015
Unraveling the structure and chemical mechanisms of highly oxygenated intermediates in oxidation of organic compounds Wang, Zhandong; Popolan-Vaida, Denisia M.; Chen, Bingjie Proceedings of the National Academy of Sciences, Vol. 114, Issue 50 https://doi.org/10.1073/pnas.1707564114	journal	November 2017
Atmospheric autoxidation is increasingly important in urban and suburban North America Praske, Eric; Otkjær, Rasmus V.; Crounse, John D. Proceedings of the National Academy of Sciences, Vol. 115, Issue 1 https://doi.org/10.1073/pnas.1715540115	journal	December 2017
Evidence that Criegee intermediates drive autoxidation in unsaturated lipids Zeng, Meirong; Heine, Nadja; Wilson, Kevin R. Proceedings of the National Academy of Sciences, Vol. 117, Issue 9 https://doi.org/10.1073/pnas.1920765117	journal	February 2020
Synthesis of methanediol [CH ₂ (OH) ₂ ]: The simplest geminal diol Zhu, Cheng; Kleimeier, N. Fabian; Turner, Andrew M. Proceedings of the National Academy of Sciences, Vol. 119, Issue 1 https://doi.org/10.1073/pnas.2111938119	journal	December 2021
Atmosphere Hydrogen Peroxide and Organic Hydroperoxides: A Review Jackson, A. V.; Hewitt, C. N. Critical Reviews in Environmental Science and Technology, Vol. 29, Issue 2 https://doi.org/10.1080/10643389991259209	journal	April 1999
Direct Kinetic Measurements of Criegee Intermediate (CH2OO) Formed by Reaction of CH2I with O2 Welz, O.; Savee, J. D.; Osborn, D. L. Science, Vol. 335, Issue 6065 https://doi.org/10.1126/science.1213229	journal	January 2012
Hydrogen Radicals, Nitrogen Radicals, and the Production of O3 in the Upper Troposphere Wennberg, P. O. Science, Vol. 279, Issue 5347 https://doi.org/10.1126/science.279.5347.49	journal	January 1998
Selective conversion of syngas to light olefins Jiao, F.; Li, J.; Pan, X. Science, Vol. 351, Issue 6277 https://doi.org/10.1126/science.aaf1835	journal	March 2016
Hydrotrioxide (ROOOH) formation in the atmosphere Berndt, Torsten; Chen, Jing; Kjærgaard, Eva R. Science, Vol. 376, Issue 6596 https://doi.org/10.1126/science.abn6012	journal	May 2022
Straightening the Hierarchical Staircase for Basis Set Extrapolations: A Low-Cost Approach to High-Accuracy Computational Chemistry Varandas, António J. C. Annual Review of Physical Chemistry, Vol. 69, Issue 1 https://doi.org/10.1146/annurev-physchem-050317-021148	journal	April 2018
Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II – gas phase reactions of organic species Atkinson, R.; Baulch, D. L.; Cox, R. A. Atmospheric Chemistry and Physics, Vol. 6, Issue 11 https://doi.org/10.5194/acp-6-3625-2006	journal	January 2006
Fragmentation inside proton-transfer-reaction-based mass spectrometers limits the detection of ROOR and ROOH peroxides Li, Haiyan; Almeida, Thomas Golin; Luo, Yuanyuan Atmospheric Measurement Techniques, Vol. 15, Issue 6 https://doi.org/10.5194/amt-15-1811-2022	journal	March 2022

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