Cargando…

Soluble/MOF-Supported Palladium Single Atoms Catalyze the Ligand-, Additive-, and Solvent-Free Aerobic Oxidation of Benzyl Alcohols to Benzoic Acids

[Image: see text] Metal single-atom catalysts (SACs) promise great rewards in terms of metal atom efficiency. However, the requirement of particular conditions and supports for their synthesis, together with the need of solvents and additives for catalytic implementation, often precludes their use u...

Descripción completa

Detalles Bibliográficos
Autores principales: Tiburcio, Estefanía, Greco, Rossella, Mon, Marta, Ballesteros-Soberanas, Jordi, Ferrando-Soria, Jesús, López-Haro, Miguel, Hernández-Garrido, Juan Carlos, Oliver-Meseguer, Judit, Marini, Carlo, Boronat, Mercedes, Armentano, Donatella, Leyva-Pérez, Antonio, Pardo, Emilio
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2021
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9645712/
https://www.ncbi.nlm.nih.gov/pubmed/33535758
http://dx.doi.org/10.1021/jacs.0c12367
_version_ 1784827014564282368
author Tiburcio, Estefanía
Greco, Rossella
Mon, Marta
Ballesteros-Soberanas, Jordi
Ferrando-Soria, Jesús
López-Haro, Miguel
Hernández-Garrido, Juan Carlos
Oliver-Meseguer, Judit
Marini, Carlo
Boronat, Mercedes
Armentano, Donatella
Leyva-Pérez, Antonio
Pardo, Emilio
author_facet Tiburcio, Estefanía
Greco, Rossella
Mon, Marta
Ballesteros-Soberanas, Jordi
Ferrando-Soria, Jesús
López-Haro, Miguel
Hernández-Garrido, Juan Carlos
Oliver-Meseguer, Judit
Marini, Carlo
Boronat, Mercedes
Armentano, Donatella
Leyva-Pérez, Antonio
Pardo, Emilio
author_sort Tiburcio, Estefanía
collection PubMed
description [Image: see text] Metal single-atom catalysts (SACs) promise great rewards in terms of metal atom efficiency. However, the requirement of particular conditions and supports for their synthesis, together with the need of solvents and additives for catalytic implementation, often precludes their use under industrially viable conditions. Here, we show that palladium single atoms are spontaneously formed after dissolving tiny amounts of palladium salts in neat benzyl alcohols, to catalyze their direct aerobic oxidation to benzoic acids without ligands, additives, or solvents. With this result in hand, the gram-scale preparation and stabilization of Pd SACs within the functional channels of a novel methyl-cysteine-based metal–organic framework (MOF) was accomplished, to give a robust and crystalline solid catalyst fully characterized with the help of single-crystal X-ray diffraction (SCXRD). These results illustrate the advantages of metal speciation in ligand-free homogeneous organic reactions and the translation into solid catalysts for potential industrial implementation.
format Online
Article
Text
id pubmed-9645712
institution National Center for Biotechnology Information
language English
publishDate 2021
publisher American Chemical Society
record_format MEDLINE/PubMed
spelling pubmed-96457122022-11-15 Soluble/MOF-Supported Palladium Single Atoms Catalyze the Ligand-, Additive-, and Solvent-Free Aerobic Oxidation of Benzyl Alcohols to Benzoic Acids Tiburcio, Estefanía Greco, Rossella Mon, Marta Ballesteros-Soberanas, Jordi Ferrando-Soria, Jesús López-Haro, Miguel Hernández-Garrido, Juan Carlos Oliver-Meseguer, Judit Marini, Carlo Boronat, Mercedes Armentano, Donatella Leyva-Pérez, Antonio Pardo, Emilio J Am Chem Soc [Image: see text] Metal single-atom catalysts (SACs) promise great rewards in terms of metal atom efficiency. However, the requirement of particular conditions and supports for their synthesis, together with the need of solvents and additives for catalytic implementation, often precludes their use under industrially viable conditions. Here, we show that palladium single atoms are spontaneously formed after dissolving tiny amounts of palladium salts in neat benzyl alcohols, to catalyze their direct aerobic oxidation to benzoic acids without ligands, additives, or solvents. With this result in hand, the gram-scale preparation and stabilization of Pd SACs within the functional channels of a novel methyl-cysteine-based metal–organic framework (MOF) was accomplished, to give a robust and crystalline solid catalyst fully characterized with the help of single-crystal X-ray diffraction (SCXRD). These results illustrate the advantages of metal speciation in ligand-free homogeneous organic reactions and the translation into solid catalysts for potential industrial implementation. American Chemical Society 2021-02-04 2021-02-17 /pmc/articles/PMC9645712/ /pubmed/33535758 http://dx.doi.org/10.1021/jacs.0c12367 Text en © 2021 American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Tiburcio, Estefanía
Greco, Rossella
Mon, Marta
Ballesteros-Soberanas, Jordi
Ferrando-Soria, Jesús
López-Haro, Miguel
Hernández-Garrido, Juan Carlos
Oliver-Meseguer, Judit
Marini, Carlo
Boronat, Mercedes
Armentano, Donatella
Leyva-Pérez, Antonio
Pardo, Emilio
Soluble/MOF-Supported Palladium Single Atoms Catalyze the Ligand-, Additive-, and Solvent-Free Aerobic Oxidation of Benzyl Alcohols to Benzoic Acids
title Soluble/MOF-Supported Palladium Single Atoms Catalyze the Ligand-, Additive-, and Solvent-Free Aerobic Oxidation of Benzyl Alcohols to Benzoic Acids
title_full Soluble/MOF-Supported Palladium Single Atoms Catalyze the Ligand-, Additive-, and Solvent-Free Aerobic Oxidation of Benzyl Alcohols to Benzoic Acids
title_fullStr Soluble/MOF-Supported Palladium Single Atoms Catalyze the Ligand-, Additive-, and Solvent-Free Aerobic Oxidation of Benzyl Alcohols to Benzoic Acids
title_full_unstemmed Soluble/MOF-Supported Palladium Single Atoms Catalyze the Ligand-, Additive-, and Solvent-Free Aerobic Oxidation of Benzyl Alcohols to Benzoic Acids
title_short Soluble/MOF-Supported Palladium Single Atoms Catalyze the Ligand-, Additive-, and Solvent-Free Aerobic Oxidation of Benzyl Alcohols to Benzoic Acids
title_sort soluble/mof-supported palladium single atoms catalyze the ligand-, additive-, and solvent-free aerobic oxidation of benzyl alcohols to benzoic acids
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9645712/
https://www.ncbi.nlm.nih.gov/pubmed/33535758
http://dx.doi.org/10.1021/jacs.0c12367
work_keys_str_mv AT tiburcioestefania solublemofsupportedpalladiumsingleatomscatalyzetheligandadditiveandsolventfreeaerobicoxidationofbenzylalcoholstobenzoicacids
AT grecorossella solublemofsupportedpalladiumsingleatomscatalyzetheligandadditiveandsolventfreeaerobicoxidationofbenzylalcoholstobenzoicacids
AT monmarta solublemofsupportedpalladiumsingleatomscatalyzetheligandadditiveandsolventfreeaerobicoxidationofbenzylalcoholstobenzoicacids
AT ballesterossoberanasjordi solublemofsupportedpalladiumsingleatomscatalyzetheligandadditiveandsolventfreeaerobicoxidationofbenzylalcoholstobenzoicacids
AT ferrandosoriajesus solublemofsupportedpalladiumsingleatomscatalyzetheligandadditiveandsolventfreeaerobicoxidationofbenzylalcoholstobenzoicacids
AT lopezharomiguel solublemofsupportedpalladiumsingleatomscatalyzetheligandadditiveandsolventfreeaerobicoxidationofbenzylalcoholstobenzoicacids
AT hernandezgarridojuancarlos solublemofsupportedpalladiumsingleatomscatalyzetheligandadditiveandsolventfreeaerobicoxidationofbenzylalcoholstobenzoicacids
AT olivermeseguerjudit solublemofsupportedpalladiumsingleatomscatalyzetheligandadditiveandsolventfreeaerobicoxidationofbenzylalcoholstobenzoicacids
AT marinicarlo solublemofsupportedpalladiumsingleatomscatalyzetheligandadditiveandsolventfreeaerobicoxidationofbenzylalcoholstobenzoicacids
AT boronatmercedes solublemofsupportedpalladiumsingleatomscatalyzetheligandadditiveandsolventfreeaerobicoxidationofbenzylalcoholstobenzoicacids
AT armentanodonatella solublemofsupportedpalladiumsingleatomscatalyzetheligandadditiveandsolventfreeaerobicoxidationofbenzylalcoholstobenzoicacids
AT leyvaperezantonio solublemofsupportedpalladiumsingleatomscatalyzetheligandadditiveandsolventfreeaerobicoxidationofbenzylalcoholstobenzoicacids
AT pardoemilio solublemofsupportedpalladiumsingleatomscatalyzetheligandadditiveandsolventfreeaerobicoxidationofbenzylalcoholstobenzoicacids