The concept of preferential atomic and molecular adsorption site is of primary relevance in heterogeneous catalysis. In the case of ultrasmall size-selected clusters, distinguishing the role played by each atom in a reaction is extremely challenging due to their reduced size and peculiar structures. Herein, it is revealed how the inequivalent atoms composing graphene-supported Pt12 and Pt13 clusters behave differently in the photoinduced dissociation of O2, with only those in the uppermost layer of the clusters being involved in the reaction. In this process, the epitaxial graphene support plays a fundamental active role: its corrugation and pinning induced by the presence of the clusters are crucial for defining the preferential adsorption site on the Pt atomic agglomerates, facili- tating the lateral diffusion of physisorbed oxygen at a distance that induces its selective adsorption in the topmost layer of the clusters, and inducing an inhomogeneous charge distribution within the clusters which directly affects the O2 adsorption. The inhomogeneous oxidation of the clusters is resolved by means of synchrotron-based X-ray photoelectron spectroscopy and supported by ab initio density functional theory calculations. The possibility to identify the active sites on Pt clusters induced by cluster–support interactions has the potential to enhance the experimentally supported design of nanocatalysts.

Unveiling Inequality of Atoms in Ultrasmall Pt Clusters: Oxygen Adsorption Limited to the Uppermost Atomic Layer

Loi, Federico
Primo
Membro del Collaboration Group
;
Bignardi, Luca
Membro del Collaboration Group
;
Perco, Deborah
Membro del Collaboration Group
;
Berti, Andrea
Membro del Collaboration Group
;
Baraldi, Alessandro
Ultimo
Membro del Collaboration Group
2024-01-01

Abstract

The concept of preferential atomic and molecular adsorption site is of primary relevance in heterogeneous catalysis. In the case of ultrasmall size-selected clusters, distinguishing the role played by each atom in a reaction is extremely challenging due to their reduced size and peculiar structures. Herein, it is revealed how the inequivalent atoms composing graphene-supported Pt12 and Pt13 clusters behave differently in the photoinduced dissociation of O2, with only those in the uppermost layer of the clusters being involved in the reaction. In this process, the epitaxial graphene support plays a fundamental active role: its corrugation and pinning induced by the presence of the clusters are crucial for defining the preferential adsorption site on the Pt atomic agglomerates, facili- tating the lateral diffusion of physisorbed oxygen at a distance that induces its selective adsorption in the topmost layer of the clusters, and inducing an inhomogeneous charge distribution within the clusters which directly affects the O2 adsorption. The inhomogeneous oxidation of the clusters is resolved by means of synchrotron-based X-ray photoelectron spectroscopy and supported by ab initio density functional theory calculations. The possibility to identify the active sites on Pt clusters induced by cluster–support interactions has the potential to enhance the experimentally supported design of nanocatalysts.
2024
ago-2024
Pubblicato
File in questo prodotto:
File Dimensione Formato  
Small Structures - 2024 - Loi - Unveiling Inequality of Atoms in Ultrasmall Pt Clusters Oxygen Adsorption Limited to the.pdf

accesso aperto

Tipologia: Documento in Versione Editoriale
Licenza: Creative commons
Dimensione 3.27 MB
Formato Adobe PDF
3.27 MB Adobe PDF Visualizza/Apri
Pubblicazioni consigliate

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11368/3091518
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 0
  • ???jsp.display-item.citation.isi??? 0
social impact