Reactive pathways toward parasitic release of singlet oxygen in metal-air batteries

Abstract The superoxide disproportionation reaction is a key step in the chemistry of aprotic metal oxygen batteries that controls the peroxide formation upon discharge and opens the way for singlet oxygen release. Here we clarify the energy landscape of the disproportionation of superoxide in aprot...

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Autores principales:	Adriano Pierini, Sergio Brutti, Enrico Bodo
Formato:	article
Lenguaje:	EN
Publicado:	Nature Portfolio 2021
Materias:	Materials of engineering and construction. Mechanics of materials TA401-492 Computer software QA76.75-76.765
Acceso en línea:	https://doaj.org/article/093a818e99f7458e81eebd9ea73cf104
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spelling	oai:doaj.org-article:093a818e99f7458e81eebd9ea73cf1042021-12-02T16:27:54ZReactive pathways toward parasitic release of singlet oxygen in metal-air batteries10.1038/s41524-021-00597-32057-3960https://doaj.org/article/093a818e99f7458e81eebd9ea73cf1042021-08-01T00:00:00Zhttps://doi.org/10.1038/s41524-021-00597-3https://doaj.org/toc/2057-3960Abstract The superoxide disproportionation reaction is a key step in the chemistry of aprotic metal oxygen batteries that controls the peroxide formation upon discharge and opens the way for singlet oxygen release. Here we clarify the energy landscape of the disproportionation of superoxide in aprotic media catalyzed by group 1A cations. Our analysis is based on ab initio multireference computational methods and unveils the competition between the expected reactive path leading to peroxide and an unexpected reaction channel that involves the reduction of the alkaline ion. Both channels lead to the release of triplet and singlet O2. The existence of this reduction channel not only facilitates singlet oxygen release but leads to a reactive neutral solvated species that can onset parasitic chemistries due to their well-known reducing properties. Overall, we show that the application of moderate overpotentials makes both these channels accessible in aprotic batteries.Adriano PieriniSergio BruttiEnrico BodoNature PortfolioarticleMaterials of engineering and construction. Mechanics of materialsTA401-492Computer softwareQA76.75-76.765ENnpj Computational Materials, Vol 7, Iss 1, Pp 1-8 (2021)
institution	DOAJ
collection	DOAJ
language	EN
topic	Materials of engineering and construction. Mechanics of materials TA401-492 Computer software QA76.75-76.765
spellingShingle	Materials of engineering and construction. Mechanics of materials TA401-492 Computer software QA76.75-76.765 Adriano Pierini Sergio Brutti Enrico Bodo Reactive pathways toward parasitic release of singlet oxygen in metal-air batteries
description	Abstract The superoxide disproportionation reaction is a key step in the chemistry of aprotic metal oxygen batteries that controls the peroxide formation upon discharge and opens the way for singlet oxygen release. Here we clarify the energy landscape of the disproportionation of superoxide in aprotic media catalyzed by group 1A cations. Our analysis is based on ab initio multireference computational methods and unveils the competition between the expected reactive path leading to peroxide and an unexpected reaction channel that involves the reduction of the alkaline ion. Both channels lead to the release of triplet and singlet O2. The existence of this reduction channel not only facilitates singlet oxygen release but leads to a reactive neutral solvated species that can onset parasitic chemistries due to their well-known reducing properties. Overall, we show that the application of moderate overpotentials makes both these channels accessible in aprotic batteries.
format	article
author	Adriano Pierini Sergio Brutti Enrico Bodo
author_facet	Adriano Pierini Sergio Brutti Enrico Bodo
author_sort	Adriano Pierini
title	Reactive pathways toward parasitic release of singlet oxygen in metal-air batteries
title_short	Reactive pathways toward parasitic release of singlet oxygen in metal-air batteries
title_full	Reactive pathways toward parasitic release of singlet oxygen in metal-air batteries
title_fullStr	Reactive pathways toward parasitic release of singlet oxygen in metal-air batteries
title_full_unstemmed	Reactive pathways toward parasitic release of singlet oxygen in metal-air batteries
title_sort	reactive pathways toward parasitic release of singlet oxygen in metal-air batteries
publisher	Nature Portfolio
publishDate	2021
url	https://doaj.org/article/093a818e99f7458e81eebd9ea73cf104
work_keys_str_mv	AT adrianopierini reactivepathwaystowardparasiticreleaseofsingletoxygeninmetalairbatteries AT sergiobrutti reactivepathwaystowardparasiticreleaseofsingletoxygeninmetalairbatteries AT enricobodo reactivepathwaystowardparasiticreleaseofsingletoxygeninmetalairbatteries
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Reactive pathways toward parasitic release of singlet oxygen in metal-air batteries

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