RT Journal Article
T1 Stability and Reversible Oxidation of Sub‐Nanometric Cu5 Metal Clusters: Integrated Experimental Study and Theoretical Modeling**
A1 Buceta Fernández, David
A1 Huseyinova, Shahana
A1 Cuerva Vidales, Miguel
A1 Lozano, Héctor
A1 Giovanetti, Lisandro J.
A1 Ramallo López, José Martín
A1 López‐Caballero, Patricia
A1 Zanchet, Alexandre
A1 Mitrushchenkov, Alexander O.
A1 Hauser, Andreas W.
A1 Barone, Giampaolo
A1 Huck‐Iriart, Cristián
A1 Escudero, Carlos
A1 Hernández‐Garrido, Juan Carlos
A1 Calvino Gámez, José Juan
A1 López‐Haro, Miguel
A1 Lara Castells, María Pilar de
A1 Requejo, Félix G.
A1 López Quintela, Manuel Arturo
K1 Density functional calculations
K1 Nanotechnology
K1 Oxidation
K1 Photoelectron spectroscopy
K1 X-ray absorption spectroscopy
AB 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 Cu5 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 O2 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 Cu5-oxygen system is presented, clearly different from the already known bulk and nano-structured chemistry of Cu
PB Wiley
SN 0947-6539
YR 2023
FD 2023-07-07
LK http://hdl.handle.net/10347/31188
UL http://hdl.handle.net/10347/31188
LA eng
NO Chem. Eur. J. 2023, 29, e202301517
NO This work has been partly supported by the Spanish Ministerio de Ciencia e Innovación (TED2021-131899B−I00/MCIN/AEI/10.13039/501100011033 / Unión Europea NextGenerationEU/PRTR), and the Agencia Estatal de Investigación (AEI) and the Fondo Europeo de Desarrollo Regional (FEDER, UE) under Grants Nos, PID2019-107115GB−C21, and PID2020-117605GB−I00; the EU Doctoral Network PHYMOL 101073474 (project call reference HORIZON-MSCA-2021-DN-01); the Austrian Science Fund (FWF) under Grant P29893-N36; XUNTA DE GALICIA (Spain) (Grupos Ref. Comp. 2021 - ED431 C 2021/16); ANPCyT PICT (2017-1220, 2017-3944 and 2019-0784) and UNLP (Project 11/X937), Argentina. This publication is also based upon work of COST Action CA21101 “Confined molecular systems: from a new generation of materials to the stars” (COSY) supported by COST (European Cooperation in Science and Technology)
DS Minerva
RD 28 abr 2026