Stability and Reversible Oxidation of Sub‐Nanometric Cu5 Metal Clusters: Integrated Experimental Study and Theoretical Modeling**

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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 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.
Funding Information
  • Agencia Nacional de Promoción Científica y Tecnológica (PICT 2017-1220, PICT 2017-3944, PICT 2019-0784)
  • Agencia Estatal de Investigación (PID2019-107115GB-C21, PID2020-117605GB-I00)
  • Austrian Science Fund (P29893-N36)
  • European Cooperation in Science and Technology (CM1405 "Molecules in Motion" (MOLIM), COST Action CA21101 "Confined molecular systems: from a new generation of materialsto the stars")
  • Xunta de Galicia (Grupos Ref. Comp. 2021 - ED431C 2021/16)
  • Universidad Nacional de La Plata (11/X937)
  • Ministerio de Ciencia, Innovación y Universidades (TED2021-131899B-I00/MCIN/AEI/10.13039/501100011033/ Unión Europea NextGenerationEU/PRTR)
  • HORIZON EUROPE Framework Programme (EU Doctoral Network PHYMOL 101073474 (project call reference HORIZON-MSCA-2021-DN-01)

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