Experiment and Theory Clarify: Sc+ Receives One Oxygen Atom from SO2 to Form ScO+, which Proves to be a Catalyst for the Hidden Oxygen-Exchange with SO2
dc.contributor.author | Mercero Larraza, José María | |
dc.contributor.author | Rezabal Astigarraga, Elixabete | |
dc.contributor.author | Ugalde Uribe-Etxebarria, Jesús | |
dc.contributor.author | Weiske, Thomas | |
dc.contributor.author | Li, Jilai | |
dc.date.accessioned | 2022-05-11T08:21:51Z | |
dc.date.available | 2022-05-11T08:21:51Z | |
dc.date.issued | 2022-03-04 | |
dc.identifier.citation | ChemPhysChem 23(5) : (2022) // Article ID e202100773 | es_ES |
dc.identifier.issn | 1439-4235 | |
dc.identifier.issn | 1439-7641 | |
dc.identifier.uri | http://hdl.handle.net/10810/56508 | |
dc.description.abstract | [EN] Using Fourier-transform ion cyclotron resonance mass spectrometry, it was experimentally determined that Sc+ in the highly diluted gas phase reacts with SO2 to form ScO+ and SO. By O-18 labeling, ScO+ was shown to play the role of a catalyst when further reacting with SO2 in a Mars-van Krevelen-like (MvK) oxygen exchange process, where a solid catalyst actively reacts with the substrate but emerges apparently unchanged at the end of the cycle. High-level quantum chemical calculations confirmed that the multi-step process to form ScO+ and SO is exoergic and that all intermediates and transition states in between are located energetically below the entrance level. The reaction starts from the triplet surface; although three spin-crossing points with minimal energy have been identified by computational means, there is no evidence that a two-state scenario is involved in the course of the reaction, by which the reactants could switch from the triplet to the singlet surface and back. Pivotal to the oxygen exchange reaction of ScO+ with SO2 is the occurrence of a highly symmetric four-membered cyclic intermediate by which two oxygen atoms become equivalent. | es_ES |
dc.description.sponsorship | The authors thank IZO-SGI SGIker (UPV/EHU), supported by ERDF and ESF European funding programmes, for technical and human assistance with the calculations, and the DIPC for generous allocation of computational resources. Financial support comes from the Spanish Office for Scientific Research (MCIU /AEI /FEDER, UE), Ref.: PGC2018-097529-B-100 and Eusko Jaurlaritza (Basque Government), Ref.: IT1254-19, and the National Natural Science Foundation of China (21773085 and 92161120). | es_ES |
dc.language.iso | eng | es_ES |
dc.publisher | Wiley | es_ES |
dc.relation | info:eu-repo/grantAgreement/MICIU/PGC2018-097529-B-100 | es_ES |
dc.rights | info:eu-repo/semantics/openAccess | es_ES |
dc.rights.uri | http://creativecommons.org/licenses/by/3.0/es/ | * |
dc.subject | catalysis | es_ES |
dc.subject | gas-phase reactions | es_ES |
dc.subject | Mars-van Krevelen mechanism | es_ES |
dc.subject | oxygen-atom exchange | es_ES |
dc.subject | quantum chemical calculations | es_ES |
dc.title | Experiment and Theory Clarify: Sc+ Receives One Oxygen Atom from SO2 to Form ScO+, which Proves to be a Catalyst for the Hidden Oxygen-Exchange with SO2 | es_ES |
dc.type | info:eu-repo/semantics/article | es_ES |
dc.rights.holder | © 2021 The Authors. ChemPhysChem published by Wiley-VCH GmbH This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. | es_ES |
dc.rights.holder | Atribución 3.0 España | * |
dc.relation.publisherversion | https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cphc.202100773 | es_ES |
dc.identifier.doi | 10.1002/cphc.202100773 | |
dc.departamentoes | Polímeros y Materiales Avanzados: Física, Química y Tecnología | es_ES |
dc.departamentoeu | Polimero eta Material Aurreratuak: Fisika, Kimika eta Teknologia | es_ES |
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This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.