Stability and Reversible Oxidation of Sub‐Nanometric Cu 5 Metal Clusters: Integrated Experimental Study and Theoretical Modeling** - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Chemistry - A European Journal Année : 2023

Stability and Reversible Oxidation of Sub‐Nanometric Cu 5 Metal Clusters: Integrated Experimental Study and Theoretical Modeling**

David Buceta
Shahana Huseyinova
Miguel Cuerva
Héctor Lozano
Lisandro Giovanetti
José Ramallo-López
Patricia López-Caballero
Alexandre Zanchet
Andreas Hauser
Giampaolo Barone
Cristián Huck-Iriart
Carlos Escudero
Juan Carlos Hernández-Garrido
José Juan Calvino
Miguel López-Haro

Résumé

Abstract Sub‐nanometer metal clusters have special physical and chemical properties, significantly different from those of nanoparticles. However, there is a major concern about their thermal stability and susceptibility to oxidation. In situ X‐ray Absorption spectroscopy and Near Ambient Pressure X‐ray Photoelectron spectroscopy results reveal that supported Cu 5 clusters are resistant to irreversible oxidation at least up to 773 K, even in the presence of 0.15 mbar of oxygen. These experimental findings can be formally described by a theoretical model which combines dispersion‐corrected DFT and first principles thermochemistry revealing that most of the adsorbed O 2 molecules are transformed into superoxo and peroxo species by an interplay of collective charge transfer within the network of Cu atoms and large amplitude “breathing” motions. A chemical phase diagram for Cu oxidation states of the Cu 5 ‐oxygen system is presented, clearly different from the already known bulk and nano‐structured chemistry of Cu.

Domaines

Chimie

Dates et versions

hal-04254368 , version 1 (23-10-2023)

Identifiants

Citer

David Buceta, Shahana Huseyinova, Miguel Cuerva, Héctor Lozano, Lisandro Giovanetti, et al.. Stability and Reversible Oxidation of Sub‐Nanometric Cu 5 Metal Clusters: Integrated Experimental Study and Theoretical Modeling**. Chemistry - A European Journal, 2023, 29 (49), pp.e202301517. ⟨10.1002/chem.202301517⟩. ⟨hal-04254368⟩
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