(17)O-EPR determination of the structure and dynamics of copper single-metal sites in zeolites

The bonding of copper ions to lattice oxygens dictates the activity and selectivity of copper exchanged zeolites. By (17)O isotopic labelling of the zeolite framework, in conjunction with advanced EPR methodologies and DFT modelling, we determine the local structure of single site Cu(II) species, we...

Descripción completa

Detalles Bibliográficos
Autores principales: Bruzzese, Paolo Cleto, Salvadori, Enrico, Jäger, Stefan, Hartmann, Martin, Civalleri, Bartolomeo, Pöppl, Andreas, Chiesa, Mario
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2021
Materias:
Article
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8324863/
https://www.ncbi.nlm.nih.gov/pubmed/34330914
http://dx.doi.org/10.1038/s41467-021-24935-7
_version_ 1783731447818878976
author Bruzzese, Paolo Cleto
Salvadori, Enrico
Jäger, Stefan
Hartmann, Martin
Civalleri, Bartolomeo
Pöppl, Andreas
Chiesa, Mario
author_facet Bruzzese, Paolo Cleto
Salvadori, Enrico
Jäger, Stefan
Hartmann, Martin
Civalleri, Bartolomeo
Pöppl, Andreas
Chiesa, Mario
author_sort Bruzzese, Paolo Cleto
collection PubMed
description The bonding of copper ions to lattice oxygens dictates the activity and selectivity of copper exchanged zeolites. By (17)O isotopic labelling of the zeolite framework, in conjunction with advanced EPR methodologies and DFT modelling, we determine the local structure of single site Cu(II) species, we quantify the covalency of the metal-framework bond and we assess how this scenario is modified by the presence of solvating H(2)(16)O or H(2)(17)O molecules. This enables to follow the migration of Cu(II) species as a function of hydration conditions, providing evidence for a reversible transfer pathway within the zeolite cage as a function of the water pressure. The results presented in this paper establish (17)O EPR as a versatile tool for characterizing metal-oxide interactions in open-shell systems.
format Online
Article
Text
id pubmed-8324863
institution National Center for Biotechnology Information
language English
publishDate 2021
publisher Nature Publishing Group UK
record_format MEDLINE/PubMed
spelling pubmed-83248632021-08-19 (17)O-EPR determination of the structure and dynamics of copper single-metal sites in zeolites Bruzzese, Paolo Cleto Salvadori, Enrico Jäger, Stefan Hartmann, Martin Civalleri, Bartolomeo Pöppl, Andreas Chiesa, Mario Nat Commun Article The bonding of copper ions to lattice oxygens dictates the activity and selectivity of copper exchanged zeolites. By (17)O isotopic labelling of the zeolite framework, in conjunction with advanced EPR methodologies and DFT modelling, we determine the local structure of single site Cu(II) species, we quantify the covalency of the metal-framework bond and we assess how this scenario is modified by the presence of solvating H(2)(16)O or H(2)(17)O molecules. This enables to follow the migration of Cu(II) species as a function of hydration conditions, providing evidence for a reversible transfer pathway within the zeolite cage as a function of the water pressure. The results presented in this paper establish (17)O EPR as a versatile tool for characterizing metal-oxide interactions in open-shell systems. Nature Publishing Group UK 2021-07-30 /pmc/articles/PMC8324863/ /pubmed/34330914 http://dx.doi.org/10.1038/s41467-021-24935-7 Text en © The Author(s) 2021 https://creativecommons.org/licenses/by/4.0/Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) .
spellingShingle Article
Bruzzese, Paolo Cleto
Salvadori, Enrico
Jäger, Stefan
Hartmann, Martin
Civalleri, Bartolomeo
Pöppl, Andreas
Chiesa, Mario
(17)O-EPR determination of the structure and dynamics of copper single-metal sites in zeolites
title (17)O-EPR determination of the structure and dynamics of copper single-metal sites in zeolites
title_full (17)O-EPR determination of the structure and dynamics of copper single-metal sites in zeolites
title_fullStr (17)O-EPR determination of the structure and dynamics of copper single-metal sites in zeolites
title_full_unstemmed (17)O-EPR determination of the structure and dynamics of copper single-metal sites in zeolites
title_short (17)O-EPR determination of the structure and dynamics of copper single-metal sites in zeolites
title_sort (17)o-epr determination of the structure and dynamics of copper single-metal sites in zeolites
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8324863/
https://www.ncbi.nlm.nih.gov/pubmed/34330914
http://dx.doi.org/10.1038/s41467-021-24935-7
work_keys_str_mv AT bruzzesepaolocleto 17oeprdeterminationofthestructureanddynamicsofcoppersinglemetalsitesinzeolites
AT salvadorienrico 17oeprdeterminationofthestructureanddynamicsofcoppersinglemetalsitesinzeolites
AT jagerstefan 17oeprdeterminationofthestructureanddynamicsofcoppersinglemetalsitesinzeolites
AT hartmannmartin 17oeprdeterminationofthestructureanddynamicsofcoppersinglemetalsitesinzeolites
AT civalleribartolomeo 17oeprdeterminationofthestructureanddynamicsofcoppersinglemetalsitesinzeolites
AT popplandreas 17oeprdeterminationofthestructureanddynamicsofcoppersinglemetalsitesinzeolites
AT chiesamario 17oeprdeterminationofthestructureanddynamicsofcoppersinglemetalsitesinzeolites

Ejemplares similares