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

Autor: Buceta D; Department of Physical Chemistry, Nanomag Laboratory, Universidad de Santiago de Compostela, 15782, Santiago de Compostela, Spain., Huseyinova S; Department of Physical Chemistry, Nanomag Laboratory, Universidad de Santiago de Compostela, 15782, Santiago de Compostela, Spain., Cuerva M; Department of Physical Chemistry, Nanomag Laboratory, Universidad de Santiago de Compostela, 15782, Santiago de Compostela, Spain., Lozano H; Department of Physical Chemistry, Nanomag Laboratory, Universidad de Santiago de Compostela, 15782, Santiago de Compostela, Spain., Giovanetti LJ; Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas (INIFTA), Dto. de Química, Facultad de Ciencias Exactas, UNLP and CONICET, Diag. 113 y 64., 1900, La Plata, Argentina., Ramallo-López JM; Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas (INIFTA), Dto. de Química, Facultad de Ciencias Exactas, UNLP and CONICET, Diag. 113 y 64., 1900, La Plata, Argentina., López-Caballero P; Instituto de Física Fundamental (AbinitSim Unit), CSIC, Serrano 123, 28006, Madrid, Spain., Zanchet A; Instituto de Física Fundamental (AbinitSim Unit), CSIC, Serrano 123, 28006, Madrid, Spain., Mitrushchenkov AO; MSME, Univ Gustave Eiffel, UPEC, CNRS, 77454, Marne-la-Vallée, France., Hauser AW; Institute of Experimental Physics, Graz University of Technology, Petersgasse 16, 8010, Graz, Austria., Barone G; Department of Biological, Chemical and Pharmaceutical Sciences and Technologies, University of Palermo, 90128, Palermo, Italy., Huck-Iriart C; Laboratorio de Cristalografía Aplicada, Escuela de Ciencia y Tecnología, Universidad Nacional de San Martín (UNSAM), Campus Miguelete, 25 de Mayo y Francia, 1650, San Martín, Provincia, Buenos Aires, Argentina.; ALBA Synchrotron Light Source, Carrer de la Llum 2-26, 08290, Cerdanyola del Vallès, Barcelona, Spain., Escudero C; ALBA Synchrotron Light Source, Carrer de la Llum 2-26, 08290, Cerdanyola del Vallès, Barcelona, Spain., Hernández-Garrido JC; Department of Material Science and Metallurgic Engineering and Inorganic Chemistry, Faculty of Science, University of Cádiz, 11510, Puerto Real, Cádiz, Spain., Calvino JJ; Department of Material Science and Metallurgic Engineering and Inorganic Chemistry, Faculty of Science, University of Cádiz, 11510, Puerto Real, Cádiz, Spain., López-Haro M; Department of Material Science and Metallurgic Engineering and Inorganic Chemistry, Faculty of Science, University of Cádiz, 11510, Puerto Real, Cádiz, Spain., de Lara-Castells MP; Instituto de Física Fundamental (AbinitSim Unit), CSIC, Serrano 123, 28006, Madrid, Spain., Requejo FG; Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas (INIFTA), Dto. de Química, Facultad de Ciencias Exactas, UNLP and CONICET, Diag. 113 y 64., 1900, La Plata, Argentina., López-Quintela MA; Department of Physical Chemistry, Nanomag Laboratory, Universidad de Santiago de Compostela, 15782, Santiago de Compostela, Spain.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2023 Sep 01; Vol. 29 (49), pp. e202301517. Date of Electronic Publication: 2023 Jul 07.
DOI: 10.1002/chem.202301517
Abstrakt: 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.
(© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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