Mechanism of mediated alkali peroxide oxidation and triplet versus singlet oxygen formation
Samo za registrovane korisnike
2021
Autori
Petit, Yann K.Mourad, Eleonore
Prehal, Christian
Leypold, Christian
Windischbacher, Andreas
Mijailović, Daniel
Slugovc, Christian
Borisov, Sergey M.
Zojer, Egbert
Brutti, Sergio
Fontaine, Olivier
Freunberger, Stefan A.
Članak u časopisu (Objavljena verzija)
Metapodaci
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Aprotic alkali metal-O-2 batteries face two major obstacles to their chemistry occurring efficiently, the insulating nature of the formed alkali superoxides/peroxides and parasitic reactions that are caused by the highly reactive singlet oxygen (O-1(2)). Redox mediators are recognized to be key for improving rechargeability. However, it is unclear how they affect O-1(2) formation, which hinders strategies for their improvement. Here we clarify the mechanism of mediated peroxide and superoxide oxidation and thus explain how redox mediators either enhance or suppress O-1(2) formation. We show that charging commences with peroxide oxidation to a superoxide intermediate and that redox potentials above similar to 3.5 V versus Li/Li+ drive O-1(2) evolution from superoxide oxidation, while disproportionation always generates some O-1(2). We find that O-1(2) suppression requires oxidation to be faster than the generation of O-1(2) from disproportionation. Oxidation rates decrease with growing ...driving force following Marcus inverted-region behaviour, establishing a region of maximum rate.
Izvor:
Nature Chemistry, 2021, 13, 5, 465-471Izdavač:
- Nature Research
Finansiranje / projekti:
- European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (grant agreement No. 636069)
- French National Research Agency (STORE-EX Labex Project ANR-10-LABX-76-01)
DOI: 10.1038/s41557-021-00643-z
ISSN: 1755-4330
PubMed: 33723377
WoS: 000629296400001
Scopus: 2-s2.0-85102822983
Institucija/grupa
Tehnološko-metalurški fakultetTY - JOUR AU - Petit, Yann K. AU - Mourad, Eleonore AU - Prehal, Christian AU - Leypold, Christian AU - Windischbacher, Andreas AU - Mijailović, Daniel AU - Slugovc, Christian AU - Borisov, Sergey M. AU - Zojer, Egbert AU - Brutti, Sergio AU - Fontaine, Olivier AU - Freunberger, Stefan A. PY - 2021 UR - http://TechnoRep.tmf.bg.ac.rs/handle/123456789/4903 AB - Aprotic alkali metal-O-2 batteries face two major obstacles to their chemistry occurring efficiently, the insulating nature of the formed alkali superoxides/peroxides and parasitic reactions that are caused by the highly reactive singlet oxygen (O-1(2)). Redox mediators are recognized to be key for improving rechargeability. However, it is unclear how they affect O-1(2) formation, which hinders strategies for their improvement. Here we clarify the mechanism of mediated peroxide and superoxide oxidation and thus explain how redox mediators either enhance or suppress O-1(2) formation. We show that charging commences with peroxide oxidation to a superoxide intermediate and that redox potentials above similar to 3.5 V versus Li/Li+ drive O-1(2) evolution from superoxide oxidation, while disproportionation always generates some O-1(2). We find that O-1(2) suppression requires oxidation to be faster than the generation of O-1(2) from disproportionation. Oxidation rates decrease with growing driving force following Marcus inverted-region behaviour, establishing a region of maximum rate. PB - Nature Research T2 - Nature Chemistry T1 - Mechanism of mediated alkali peroxide oxidation and triplet versus singlet oxygen formation EP - 471 IS - 5 SP - 465 VL - 13 DO - 10.1038/s41557-021-00643-z ER -
@article{ author = "Petit, Yann K. and Mourad, Eleonore and Prehal, Christian and Leypold, Christian and Windischbacher, Andreas and Mijailović, Daniel and Slugovc, Christian and Borisov, Sergey M. and Zojer, Egbert and Brutti, Sergio and Fontaine, Olivier and Freunberger, Stefan A.", year = "2021", abstract = "Aprotic alkali metal-O-2 batteries face two major obstacles to their chemistry occurring efficiently, the insulating nature of the formed alkali superoxides/peroxides and parasitic reactions that are caused by the highly reactive singlet oxygen (O-1(2)). Redox mediators are recognized to be key for improving rechargeability. However, it is unclear how they affect O-1(2) formation, which hinders strategies for their improvement. Here we clarify the mechanism of mediated peroxide and superoxide oxidation and thus explain how redox mediators either enhance or suppress O-1(2) formation. We show that charging commences with peroxide oxidation to a superoxide intermediate and that redox potentials above similar to 3.5 V versus Li/Li+ drive O-1(2) evolution from superoxide oxidation, while disproportionation always generates some O-1(2). We find that O-1(2) suppression requires oxidation to be faster than the generation of O-1(2) from disproportionation. Oxidation rates decrease with growing driving force following Marcus inverted-region behaviour, establishing a region of maximum rate.", publisher = "Nature Research", journal = "Nature Chemistry", title = "Mechanism of mediated alkali peroxide oxidation and triplet versus singlet oxygen formation", pages = "471-465", number = "5", volume = "13", doi = "10.1038/s41557-021-00643-z" }
Petit, Y. K., Mourad, E., Prehal, C., Leypold, C., Windischbacher, A., Mijailović, D., Slugovc, C., Borisov, S. M., Zojer, E., Brutti, S., Fontaine, O.,& Freunberger, S. A.. (2021). Mechanism of mediated alkali peroxide oxidation and triplet versus singlet oxygen formation. in Nature Chemistry Nature Research., 13(5), 465-471. https://doi.org/10.1038/s41557-021-00643-z
Petit YK, Mourad E, Prehal C, Leypold C, Windischbacher A, Mijailović D, Slugovc C, Borisov SM, Zojer E, Brutti S, Fontaine O, Freunberger SA. Mechanism of mediated alkali peroxide oxidation and triplet versus singlet oxygen formation. in Nature Chemistry. 2021;13(5):465-471. doi:10.1038/s41557-021-00643-z .
Petit, Yann K., Mourad, Eleonore, Prehal, Christian, Leypold, Christian, Windischbacher, Andreas, Mijailović, Daniel, Slugovc, Christian, Borisov, Sergey M., Zojer, Egbert, Brutti, Sergio, Fontaine, Olivier, Freunberger, Stefan A., "Mechanism of mediated alkali peroxide oxidation and triplet versus singlet oxygen formation" in Nature Chemistry, 13, no. 5 (2021):465-471, https://doi.org/10.1038/s41557-021-00643-z . .