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The highest oxidation state observed in graphene-supported sub-nanometer iron oxide clusters

Size-selected iron oxide nanoclusters are outstanding candidates for technological-oriented applications due to their high efficiency-to-cost ratio. However, despite many theoretical studies, experimental works on their oxidation mechanism are still limited to gas-phase clusters. Herein we investiga...

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Autores principales: Perco, Deborah, Loi, Federico, Bignardi, Luca, Sbuelz, Luca, Lacovig, Paolo, Tosi, Ezequiel, Lizzit, Silvano, Kartouzian, Aras, Heiz, Ueli, Baraldi, Alessandro
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10070315/
https://www.ncbi.nlm.nih.gov/pubmed/37012362
http://dx.doi.org/10.1038/s42004-023-00865-x
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author Perco, Deborah
Loi, Federico
Bignardi, Luca
Sbuelz, Luca
Lacovig, Paolo
Tosi, Ezequiel
Lizzit, Silvano
Kartouzian, Aras
Heiz, Ueli
Baraldi, Alessandro
author_facet Perco, Deborah
Loi, Federico
Bignardi, Luca
Sbuelz, Luca
Lacovig, Paolo
Tosi, Ezequiel
Lizzit, Silvano
Kartouzian, Aras
Heiz, Ueli
Baraldi, Alessandro
author_sort Perco, Deborah
collection PubMed
description Size-selected iron oxide nanoclusters are outstanding candidates for technological-oriented applications due to their high efficiency-to-cost ratio. However, despite many theoretical studies, experimental works on their oxidation mechanism are still limited to gas-phase clusters. Herein we investigate the oxidation of graphene-supported size-selected Fe(n) clusters by means of high-resolution X-ray Photoelectron Spectroscopy. We show a dependency of the core electron Fe 2p(3/2) binding energy of metallic and oxidized clusters on the cluster size. Binding energies are also linked to chemical reactivity through the asymmetry parameter which is related to electron density of states at the Fermi energy. Upon oxidation, iron atoms in clusters reach the oxidation state Fe(II) and the absence of other oxidation states indicates a Fe-to-O ratio close to 1:1, in agreement with previous theoretical calculations and gas-phase experiments. Such knowledge can provide a basis for a better understanding of the behavior of iron oxide nanoclusters as supported catalysts.
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spelling pubmed-100703152023-04-05 The highest oxidation state observed in graphene-supported sub-nanometer iron oxide clusters Perco, Deborah Loi, Federico Bignardi, Luca Sbuelz, Luca Lacovig, Paolo Tosi, Ezequiel Lizzit, Silvano Kartouzian, Aras Heiz, Ueli Baraldi, Alessandro Commun Chem Article Size-selected iron oxide nanoclusters are outstanding candidates for technological-oriented applications due to their high efficiency-to-cost ratio. However, despite many theoretical studies, experimental works on their oxidation mechanism are still limited to gas-phase clusters. Herein we investigate the oxidation of graphene-supported size-selected Fe(n) clusters by means of high-resolution X-ray Photoelectron Spectroscopy. We show a dependency of the core electron Fe 2p(3/2) binding energy of metallic and oxidized clusters on the cluster size. Binding energies are also linked to chemical reactivity through the asymmetry parameter which is related to electron density of states at the Fermi energy. Upon oxidation, iron atoms in clusters reach the oxidation state Fe(II) and the absence of other oxidation states indicates a Fe-to-O ratio close to 1:1, in agreement with previous theoretical calculations and gas-phase experiments. Such knowledge can provide a basis for a better understanding of the behavior of iron oxide nanoclusters as supported catalysts. Nature Publishing Group UK 2023-04-03 /pmc/articles/PMC10070315/ /pubmed/37012362 http://dx.doi.org/10.1038/s42004-023-00865-x Text en © The Author(s) 2023 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
Perco, Deborah
Loi, Federico
Bignardi, Luca
Sbuelz, Luca
Lacovig, Paolo
Tosi, Ezequiel
Lizzit, Silvano
Kartouzian, Aras
Heiz, Ueli
Baraldi, Alessandro
The highest oxidation state observed in graphene-supported sub-nanometer iron oxide clusters
title The highest oxidation state observed in graphene-supported sub-nanometer iron oxide clusters
title_full The highest oxidation state observed in graphene-supported sub-nanometer iron oxide clusters
title_fullStr The highest oxidation state observed in graphene-supported sub-nanometer iron oxide clusters
title_full_unstemmed The highest oxidation state observed in graphene-supported sub-nanometer iron oxide clusters
title_short The highest oxidation state observed in graphene-supported sub-nanometer iron oxide clusters
title_sort highest oxidation state observed in graphene-supported sub-nanometer iron oxide clusters
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10070315/
https://www.ncbi.nlm.nih.gov/pubmed/37012362
http://dx.doi.org/10.1038/s42004-023-00865-x
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