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

Luca Artiglia; Jacinta Edebeli; Fabrizio Orlando; Shuzhen Chen; Ming Tao Lee; Pablo Corral Arroyo; Anina Gilgen; Thorsten Bartels-Rausch; Armin Kleibert; Mario Vazdar; Marcelo Andres Carignano; Joseph S. Francisco; Paul B. Shepson; Ivan Gladich; Markus Ammann

doi:10.1038/s41467-017-00823-x

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

Luca Artiglia, Jacinta Edebeli, Fabrizio Orlando, Shuzhen Chen, Ming Tao Lee, Pablo Corral Arroyo, Anina Gilgen, Thorsten Bartels-Rausch, Armin Kleibert, Mario Vazdar, Marcelo Andres Carignano, Joseph S. Francisco, Paul B. Shepson, Ivan Gladich, Markus Ammann

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65 Scopus citations

Abstract

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.

Original language	English (US)
Journal	Nature Communications
Volume	8
Issue number	1
DOIs	https://doi.org/10.1038/s41467-017-00823-x
State	Published - Sep 26 2017
Externally published	Yes

Bibliographical note

KAUST Repository Item: Exported on 2022-06-08
Acknowledgements: For computer time, this research used the resources of the Supercomputing Laboratory at King Abdullah University of Science and Technology (KAUST) in Thuwal, Saudi Arabia. The engineering work and technical support by Mario Birrer is greatly acknowledged. J.E. acknowledges the Swiss National Science Foundation (SNF), grant 155999. M.A., F.O. and S.C. acknowledge funding by the Swiss National Science Foundation (grants no 149492 and 169176). We thank Michel Rossi for providing the ozone generator.
This publication acknowledges KAUST support, but has no KAUST affiliated authors.

ASJC Scopus subject areas

General Biochemistry, Genetics and Molecular Biology
General Chemistry
General Physics and Astronomy

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10.1038/s41467-017-00823-x

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Artiglia, L., Edebeli, J., Orlando, F., Chen, S., Lee, M. T., Corral Arroyo, P., Gilgen, A., Bartels-Rausch, T., Kleibert, A., Vazdar, M., Andres Carignano, M., Francisco, J. S., Shepson, P. B., Gladich, I., & Ammann, M. (2017). A surface-stabilized ozonide triggers bromide oxidation at the aqueous solution-vapour interface. Nature Communications, 8(1). https://doi.org/10.1038/s41467-017-00823-x

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title = "A surface-stabilized ozonide triggers bromide oxidation at the aqueous solution-vapour interface",

abstract = "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.",

author = "Luca Artiglia and Jacinta Edebeli and Fabrizio Orlando and Shuzhen Chen and Lee, {Ming Tao} and {Corral Arroyo}, Pablo and Anina Gilgen and Thorsten Bartels-Rausch and Armin Kleibert and Mario Vazdar and {Andres Carignano}, Marcelo and Francisco, {Joseph S.} and Shepson, {Paul B.} and Ivan Gladich and Markus Ammann",

note = "KAUST Repository Item: Exported on 2022-06-08 Acknowledgements: For computer time, this research used the resources of the Supercomputing Laboratory at King Abdullah University of Science and Technology (KAUST) in Thuwal, Saudi Arabia. The engineering work and technical support by Mario Birrer is greatly acknowledged. J.E. acknowledges the Swiss National Science Foundation (SNF), grant 155999. M.A., F.O. and S.C. acknowledge funding by the Swiss National Science Foundation (grants no 149492 and 169176). We thank Michel Rossi for providing the ozone generator. This publication acknowledges KAUST support, but has no KAUST affiliated authors.",

year = "2017",

month = sep,

day = "26",

doi = "10.1038/s41467-017-00823-x",

language = "English (US)",

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Artiglia, L, Edebeli, J, Orlando, F, Chen, S, Lee, MT, Corral Arroyo, P, Gilgen, A, Bartels-Rausch, T, Kleibert, A, Vazdar, M, Andres Carignano, M, Francisco, JS, Shepson, PB, Gladich, I & Ammann, M 2017, 'A surface-stabilized ozonide triggers bromide oxidation at the aqueous solution-vapour interface', Nature Communications, vol. 8, no. 1. https://doi.org/10.1038/s41467-017-00823-x

TY - JOUR

T1 - A surface-stabilized ozonide triggers bromide oxidation at the aqueous solution-vapour interface

AU - Artiglia, Luca

AU - Edebeli, Jacinta

AU - Orlando, Fabrizio

AU - Chen, Shuzhen

AU - Lee, Ming Tao

AU - Corral Arroyo, Pablo

AU - Gilgen, Anina

AU - Bartels-Rausch, Thorsten

AU - Kleibert, Armin

AU - Vazdar, Mario

AU - Andres Carignano, Marcelo

AU - Francisco, Joseph S.

AU - Shepson, Paul B.

AU - Gladich, Ivan

AU - Ammann, Markus

N1 - KAUST Repository Item: Exported on 2022-06-08 Acknowledgements: For computer time, this research used the resources of the Supercomputing Laboratory at King Abdullah University of Science and Technology (KAUST) in Thuwal, Saudi Arabia. The engineering work and technical support by Mario Birrer is greatly acknowledged. J.E. acknowledges the Swiss National Science Foundation (SNF), grant 155999. M.A., F.O. and S.C. acknowledge funding by the Swiss National Science Foundation (grants no 149492 and 169176). We thank Michel Rossi for providing the ozone generator. This publication acknowledges KAUST support, but has no KAUST affiliated authors.

PY - 2017/9/26

Y1 - 2017/9/26

N2 - 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.

AB - 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.

UR - http://hdl.handle.net/10754/678745

UR - http://www.nature.com/articles/s41467-017-00823-x

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U2 - 10.1038/s41467-017-00823-x

DO - 10.1038/s41467-017-00823-x

M3 - Article

C2 - 28951540

SN - 2041-1723

VL - 8

JO - Nature Communications

JF - Nature Communications

IS - 1

ER -

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

Abstract

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