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Does Cluster Encapsulation Inhibit Sintering? Stabilization of Size-Selected Pt Clusters on Fe(3)O(4)(001) by SMSI

[Image: see text] The metastability of supported metal nanoparticles limits their application in heterogeneous catalysis at elevated temperatures due to their tendency to sinter. One strategy to overcome these thermodynamic limits on reducible oxide supports is encapsulation via strong metal–support...

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Autores principales: Kaiser, Sebastian, Plansky, Johanna, Krinninger, Matthias, Shavorskiy, Andrey, Zhu, Suyun, Heiz, Ueli, Esch, Friedrich, Lechner, Barbara A. J.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10167661/
https://www.ncbi.nlm.nih.gov/pubmed/37180966
http://dx.doi.org/10.1021/acscatal.3c00448
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author Kaiser, Sebastian
Plansky, Johanna
Krinninger, Matthias
Shavorskiy, Andrey
Zhu, Suyun
Heiz, Ueli
Esch, Friedrich
Lechner, Barbara A. J.
author_facet Kaiser, Sebastian
Plansky, Johanna
Krinninger, Matthias
Shavorskiy, Andrey
Zhu, Suyun
Heiz, Ueli
Esch, Friedrich
Lechner, Barbara A. J.
author_sort Kaiser, Sebastian
collection PubMed
description [Image: see text] The metastability of supported metal nanoparticles limits their application in heterogeneous catalysis at elevated temperatures due to their tendency to sinter. One strategy to overcome these thermodynamic limits on reducible oxide supports is encapsulation via strong metal–support interaction (SMSI). While annealing-induced encapsulation is a well-explored phenomenon for extended nanoparticles, it is as yet unknown whether the same mechanisms hold for subnanometer clusters, where concomitant sintering and alloying might play a significant role. In this article, we explore the encapsulation and stability of size-selected Pt(5), Pt(10), and Pt(19) clusters deposited on Fe(3)O(4)(001). In a multimodal approach using temperature-programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS), and scanning tunneling microscopy (STM), we demonstrate that SMSI indeed leads to the formation of a defective, FeO-like conglomerate encapsulating the clusters. By stepwise annealing up to 1023 K, we observe the succession of encapsulation, cluster coalescence, and Ostwald ripening, resulting in square-shaped crystalline Pt particles, independent of the initial cluster size. The respective sintering onset temperatures scale with the cluster footprint and thus size. Remarkably, while small encapsulated clusters can still diffuse as a whole, atom detachment and thus Ostwald ripening are successfully suppressed up to 823 K, i.e., 200 K above the Hüttig temperature that indicates the thermodynamic stability limit.
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spelling pubmed-101676612023-05-10 Does Cluster Encapsulation Inhibit Sintering? Stabilization of Size-Selected Pt Clusters on Fe(3)O(4)(001) by SMSI Kaiser, Sebastian Plansky, Johanna Krinninger, Matthias Shavorskiy, Andrey Zhu, Suyun Heiz, Ueli Esch, Friedrich Lechner, Barbara A. J. ACS Catal [Image: see text] The metastability of supported metal nanoparticles limits their application in heterogeneous catalysis at elevated temperatures due to their tendency to sinter. One strategy to overcome these thermodynamic limits on reducible oxide supports is encapsulation via strong metal–support interaction (SMSI). While annealing-induced encapsulation is a well-explored phenomenon for extended nanoparticles, it is as yet unknown whether the same mechanisms hold for subnanometer clusters, where concomitant sintering and alloying might play a significant role. In this article, we explore the encapsulation and stability of size-selected Pt(5), Pt(10), and Pt(19) clusters deposited on Fe(3)O(4)(001). In a multimodal approach using temperature-programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS), and scanning tunneling microscopy (STM), we demonstrate that SMSI indeed leads to the formation of a defective, FeO-like conglomerate encapsulating the clusters. By stepwise annealing up to 1023 K, we observe the succession of encapsulation, cluster coalescence, and Ostwald ripening, resulting in square-shaped crystalline Pt particles, independent of the initial cluster size. The respective sintering onset temperatures scale with the cluster footprint and thus size. Remarkably, while small encapsulated clusters can still diffuse as a whole, atom detachment and thus Ostwald ripening are successfully suppressed up to 823 K, i.e., 200 K above the Hüttig temperature that indicates the thermodynamic stability limit. American Chemical Society 2023-04-21 /pmc/articles/PMC10167661/ /pubmed/37180966 http://dx.doi.org/10.1021/acscatal.3c00448 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by-nc-nd/4.0/Permits non-commercial access and re-use, provided that author attribution and integrity are maintained; but does not permit creation of adaptations or other derivative works (https://creativecommons.org/licenses/by-nc-nd/4.0/).
spellingShingle Kaiser, Sebastian
Plansky, Johanna
Krinninger, Matthias
Shavorskiy, Andrey
Zhu, Suyun
Heiz, Ueli
Esch, Friedrich
Lechner, Barbara A. J.
Does Cluster Encapsulation Inhibit Sintering? Stabilization of Size-Selected Pt Clusters on Fe(3)O(4)(001) by SMSI
title Does Cluster Encapsulation Inhibit Sintering? Stabilization of Size-Selected Pt Clusters on Fe(3)O(4)(001) by SMSI
title_full Does Cluster Encapsulation Inhibit Sintering? Stabilization of Size-Selected Pt Clusters on Fe(3)O(4)(001) by SMSI
title_fullStr Does Cluster Encapsulation Inhibit Sintering? Stabilization of Size-Selected Pt Clusters on Fe(3)O(4)(001) by SMSI
title_full_unstemmed Does Cluster Encapsulation Inhibit Sintering? Stabilization of Size-Selected Pt Clusters on Fe(3)O(4)(001) by SMSI
title_short Does Cluster Encapsulation Inhibit Sintering? Stabilization of Size-Selected Pt Clusters on Fe(3)O(4)(001) by SMSI
title_sort does cluster encapsulation inhibit sintering? stabilization of size-selected pt clusters on fe(3)o(4)(001) by smsi
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10167661/
https://www.ncbi.nlm.nih.gov/pubmed/37180966
http://dx.doi.org/10.1021/acscatal.3c00448
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