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

Autor: Mercedes Boronat, Antonio Leyva-Pérez, Miguel López-Haro, Rossella Greco, Emilio Pardo, Carlo Marini, Jordi Ballesteros-Soberanas, Juan C. Hernández-Garrido, Donatella Armentano, Jesús Ferrando-Soria, Marta Mon, Judit Oliver-Meseguer, Estefanía Tiburcio
Přispěvatelé: Ministerio de Economía y Competitividad (España), Ministerio de Ciencia, Innovación y Universidades (España)
Rok vydání: 2021
Předmět:
Zdroj: Journal of the American Chemical Society
Tiburcio, Estefanía Greco, Rossella Mon Conejero, 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 Marín, Emilio 2021 Soluble/MOF-Supported Palladium Single Atoms Catalyze the Ligand-, Additive-, and Solvent-Free Aerobic Oxidation of Benzyl Alcohols to Benzoic Acids Journal of the American Chemical Society 143 6 2581 2592
RODERIC. Repositorio Institucional de la Universitat de Valéncia
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Digital.CSIC. Repositorio Institucional del CSIC
ISSN: 1520-5126
Popis: 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.
This work was supported by the Ministero dell’Istruzione, dell’Università e della Ricerca (Italy) and the MINECO (Spain) (Projects PID2019−104778GB−I00, CTQ 2017–86735–P, RTC–2017–6331–5, Severo Ochoa program SEV–2016–0683 and Excellence Unit “Maria de Maeztu” CEX2019−000919−M). E.T. and M.M. thank MINECO and ITQ for the concession of a contract. D.A. acknowledges the financial support of the Fondazione CARIPLO/“Economia Circolare: ricerca per un futuro sostenibile” 2019, Project code: 2019–2090, MOCA and Diamond Light Source for awarded beamtime and provision of synchrotron radiation facilities and thanks Dr. Sarah Barnett and David Allan for their assistance at I19 beamline (Proposal No. MT18768-1). Thanks are also extended to the “2019 Post-doctoral Junior Leader-Retaining Fellowship, la Caixa Foundation (ID100010434 and fellowship code LCF/BQ/PR19/11700011” (J.F.-S.) and “La Caixa” scholarship (ID 100010434) LCF/BQ/DI19/11730029 (J.B.-S). E.P. acknowledges the financial support of the European Research Council under the European Union’s Horizon 2020 research and innovation programme/ERC Grant Agreement No 814804, MOF reactors. J.O.-M. acknowledges the Juan de la Cierva program for the concession of a contract (IJC2018-036514-I). We gratefully acknowledge to ALBA synchrotron for allocating beamtime and CLÆSS beamline staff for their technical support during our experiment. The computations were performed on the Tirant III cluster of the Servei d’Informàtica of the University of Valencia.
Databáze: OpenAIRE
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