A surface-stabilized ozonide triggers bromide oxidation at the aqueous solution-vapour interface

<p dir="ltr">Oxidation of bromide in aqueous environments initiates the formation of molecular halogen compounds, which is important for the global tropospheric ozone budget. In the aqueous bulk, oxidation of bromide by ozone involves a [Br•OOO−] complex as intermediate. Here we repo...

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Main Author: Luca Artiglia (1713652) (author)
Other Authors: Jacinta Edebeli (10586622) (author), Fabrizio Orlando (1701163) (author), Shuzhen Chen (297742) (author), Ming-Tao Lee (1568470) (author), Pablo Corral Arroyo (5465684) (author), Anina Gilgen (19479399) (author), Thorsten Bartels-Rausch (4117720) (author), Armin Kleibert (1270557) (author), Mario Vazdar (1435945) (author), Marcelo Andres Carignano (19725586) (author), Joseph S. Francisco (1414543) (author), Paul B. Shepson (1360947) (author), Ivan Gladich (1442929) (author), Markus Ammann (1600930) (author)
Published: 2017
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_version_ 1864513556563623936
author Luca Artiglia (1713652)
author2 Jacinta Edebeli (10586622)
Fabrizio Orlando (1701163)
Shuzhen Chen (297742)
Ming-Tao Lee (1568470)
Pablo Corral Arroyo (5465684)
Anina Gilgen (19479399)
Thorsten Bartels-Rausch (4117720)
Armin Kleibert (1270557)
Mario Vazdar (1435945)
Marcelo Andres Carignano (19725586)
Joseph S. Francisco (1414543)
Paul B. Shepson (1360947)
Ivan Gladich (1442929)
Markus Ammann (1600930)
author2_role author
author
author
author
author
author
author
author
author
author
author
author
author
author
author_facet Luca Artiglia (1713652)
Jacinta Edebeli (10586622)
Fabrizio Orlando (1701163)
Shuzhen Chen (297742)
Ming-Tao Lee (1568470)
Pablo Corral Arroyo (5465684)
Anina Gilgen (19479399)
Thorsten Bartels-Rausch (4117720)
Armin Kleibert (1270557)
Mario Vazdar (1435945)
Marcelo Andres Carignano (19725586)
Joseph S. Francisco (1414543)
Paul B. Shepson (1360947)
Ivan Gladich (1442929)
Markus Ammann (1600930)
author_role author
dc.creator.none.fl_str_mv Luca Artiglia (1713652)
Jacinta Edebeli (10586622)
Fabrizio Orlando (1701163)
Shuzhen Chen (297742)
Ming-Tao Lee (1568470)
Pablo Corral Arroyo (5465684)
Anina Gilgen (19479399)
Thorsten Bartels-Rausch (4117720)
Armin Kleibert (1270557)
Mario Vazdar (1435945)
Marcelo Andres Carignano (19725586)
Joseph S. Francisco (1414543)
Paul B. Shepson (1360947)
Ivan Gladich (1442929)
Markus Ammann (1600930)
dc.date.none.fl_str_mv 2017-09-26T03:00:00Z
dc.identifier.none.fl_str_mv 10.1038/s41467-017-00823-x
dc.relation.none.fl_str_mv https://figshare.com/articles/journal_contribution/A_surface-stabilized_ozonide_triggers_bromide_oxidation_at_the_aqueous_solution-vapour_interface/27088084
dc.rights.none.fl_str_mv CC BY 4.0
info:eu-repo/semantics/openAccess
dc.subject.none.fl_str_mv Chemical sciences
Organic chemistry
Earth sciences
Atmospheric sciences
Oxidation of bromide
Molecular halogen compounds
Tropospheric ozone budget
X-ray photoelectron spectroscopy
Ozonide
dc.title.none.fl_str_mv A surface-stabilized ozonide triggers bromide oxidation at the aqueous solution-vapour interface
dc.type.none.fl_str_mv Text
Journal contribution
info:eu-repo/semantics/publishedVersion
text
contribution to journal
description <p dir="ltr">Oxidation of bromide in aqueous environments initiates the formation of molecular halogen compounds, which is important for the global tropospheric ozone budget. In the aqueous bulk, oxidation of bromide by ozone involves a [Br•OOO−] complex as intermediate. Here we report liquid jet X-ray photoelectron spectroscopy measurements that provide direct experimental evidence for the ozonide and establish its propensity for the solution-vapour interface. Theoretical calculations support these findings, showing that water stabilizes the ozonide and lowers the energy of the transition state at neutral pH. Kinetic experiments confirm the dominance of the heterogeneous oxidation route established by this precursor at low, atmospherically relevant ozone concentrations. Taken together, our results provide a strong case of different reaction kinetics and mechanisms of reactions occurring at the aqueous phase-vapour interface compared with the bulk aqueous phase.</p><h2>Other Information</h2><p dir="ltr">Published in: Nature Communications<br>License: <a href="https://creativecommons.org/licenses/by/4.0" target="_blank">https://creativecommons.org/licenses/by/4.0</a><br>See article on publisher's website: <a href="https://dx.doi.org/10.1038/s41467-017-00823-x" target="_blank">https://dx.doi.org/10.1038/s41467-017-00823-x</a></p>
eu_rights_str_mv openAccess
id Manara2_e7246ac6802913b3c200c0ede79c244b
identifier_str_mv 10.1038/s41467-017-00823-x
network_acronym_str Manara2
network_name_str Manara2
oai_identifier_str oai:figshare.com:article/27088084
publishDate 2017
repository.mail.fl_str_mv
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rights_invalid_str_mv CC BY 4.0
spelling A surface-stabilized ozonide triggers bromide oxidation at the aqueous solution-vapour interfaceLuca Artiglia (1713652)Jacinta Edebeli (10586622)Fabrizio Orlando (1701163)Shuzhen Chen (297742)Ming-Tao Lee (1568470)Pablo Corral Arroyo (5465684)Anina Gilgen (19479399)Thorsten Bartels-Rausch (4117720)Armin Kleibert (1270557)Mario Vazdar (1435945)Marcelo Andres Carignano (19725586)Joseph S. Francisco (1414543)Paul B. Shepson (1360947)Ivan Gladich (1442929)Markus Ammann (1600930)Chemical sciencesOrganic chemistryEarth sciencesAtmospheric sciencesOxidation of bromideMolecular halogen compoundsTropospheric ozone budgetX-ray photoelectron spectroscopyOzonide<p dir="ltr">Oxidation of bromide in aqueous environments initiates the formation of molecular halogen compounds, which is important for the global tropospheric ozone budget. In the aqueous bulk, oxidation of bromide by ozone involves a [Br•OOO−] complex as intermediate. Here we report liquid jet X-ray photoelectron spectroscopy measurements that provide direct experimental evidence for the ozonide and establish its propensity for the solution-vapour interface. Theoretical calculations support these findings, showing that water stabilizes the ozonide and lowers the energy of the transition state at neutral pH. Kinetic experiments confirm the dominance of the heterogeneous oxidation route established by this precursor at low, atmospherically relevant ozone concentrations. Taken together, our results provide a strong case of different reaction kinetics and mechanisms of reactions occurring at the aqueous phase-vapour interface compared with the bulk aqueous phase.</p><h2>Other Information</h2><p dir="ltr">Published in: Nature Communications<br>License: <a href="https://creativecommons.org/licenses/by/4.0" target="_blank">https://creativecommons.org/licenses/by/4.0</a><br>See article on publisher's website: <a href="https://dx.doi.org/10.1038/s41467-017-00823-x" target="_blank">https://dx.doi.org/10.1038/s41467-017-00823-x</a></p>2017-09-26T03:00:00ZTextJournal contributioninfo:eu-repo/semantics/publishedVersiontextcontribution to journal10.1038/s41467-017-00823-xhttps://figshare.com/articles/journal_contribution/A_surface-stabilized_ozonide_triggers_bromide_oxidation_at_the_aqueous_solution-vapour_interface/27088084CC BY 4.0info:eu-repo/semantics/openAccessoai:figshare.com:article/270880842017-09-26T03:00:00Z
spellingShingle A surface-stabilized ozonide triggers bromide oxidation at the aqueous solution-vapour interface
Luca Artiglia (1713652)
Chemical sciences
Organic chemistry
Earth sciences
Atmospheric sciences
Oxidation of bromide
Molecular halogen compounds
Tropospheric ozone budget
X-ray photoelectron spectroscopy
Ozonide
status_str publishedVersion
title A surface-stabilized ozonide triggers bromide oxidation at the aqueous solution-vapour interface
title_full A surface-stabilized ozonide triggers bromide oxidation at the aqueous solution-vapour interface
title_fullStr A surface-stabilized ozonide triggers bromide oxidation at the aqueous solution-vapour interface
title_full_unstemmed A surface-stabilized ozonide triggers bromide oxidation at the aqueous solution-vapour interface
title_short A surface-stabilized ozonide triggers bromide oxidation at the aqueous solution-vapour interface
title_sort A surface-stabilized ozonide triggers bromide oxidation at the aqueous solution-vapour interface
topic Chemical sciences
Organic chemistry
Earth sciences
Atmospheric sciences
Oxidation of bromide
Molecular halogen compounds
Tropospheric ozone budget
X-ray photoelectron spectroscopy
Ozonide