0000000000191360
AUTHOR
Carlo Marini
Soluble/MOF-Supported Palladium Single Atoms Catalyze the Ligand-, Additive-, and Solvent-Free Aerobic Oxidation of Benzyl Alcohols to Benzoic Acids.
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-cystein…
Crystallographic and geometrical dependence of water oxidation activity in Co-based layered hydroxides
Cobalt-based layered hydroxides (LHs) stand out as one of the best families of electroactive materials for the alkaline oxygen evolution reaction (OER). However, fundamental aspects such as the influence of the crystalline structure and its connection with the geometry of the catalytic sites remains poorly understood. Thus, to address this we have conducted a thorough experimental and in silico study on the most essential Co-LHs (i.e.: ɑ-LH, β-LH and LDH) which allows us to understand the role of the layered structure and coordination environment of Co atoms on the OER performance. The ɑ-LH, containing both octahedral and tetrahedral sites, behaves as the best OER catalyst in comparison to …
Influence of crystallographic structure and metal vacancies on the oxygen evolution reaction performance of Ni-based layered hydroxides
Nickel-based layered hydroxides (LHs) are a family of efficient electrocatalysts for the alkaline oxygen evolution reaction (OER). Nevertheless, fundamental aspects such as the influence of the crystalline structure and the role of lattice distortion of the catalytic sites remain poorly understood and typically muddled. Herein, we carried out a comprehensive investigation on ɑ-LH, β-LH and LDH phases, analysing the role exerted by Ni-vacancies by means of structural, spectroscopical, in-silico and electrochemical studies. Indeed, density functional theory (DFT) calculations, in agreement with X-ray absorption spectroscopy (XAS), confirm that the presence of Ni-vacancies produces acute disto…
MOF-Stabilized Perfluorinated Palladium Cages Catalyze the Additive-Free Aerobic Oxidation of Aliphatic Alcohols to Acids
Extremely high electrophilic metal complexes, composed by a metal cation and very electron poor σ-donor ancillary ligands, are expected to be privileged catalysts for oxidation reactions in organic chemistry. However, their low lifetime prevents any use in catalysis. Here we show the synthesis of fluorinated pyridine-Pd coordinate cages within the channels of an anionic tridimensional metal-organic framework (MOF), and their use as efficient metal catalysts for the aerobic oxidation of aliphatic alcohols to carboxylic acids without any additive. Mechanistic studies strongly support that the MOF-stabilized coordination cage with perfluorinated ligands unleashes the full electrophilic potenti…
Local structural investigation of hafnia-zirconia polymorphs in powders and thin films by X-ray absorption spectroscopy
Björn Matthey (Fraunhofer IKTS, Dresden) is acknowledged for providing HfO2 and ZrO2 powders on short notice after DESY’s renowned customs office punished us. Parts of this research were carried out at Petra III at DESY, a member of the Helmholtz Association (HGF). The experiments on single Si:HfO2 thin film samples were performed at the CLAESS beamline at ALBA Synchrotron with the collaboration of ALBA staff. We would like to thank Edmund Welter for assistance (in using beamline P65) and DESY for enabling this research for proposal no. 20160591 and for travel support. T.S. acknowledges the German Research Foundation (DFG) for funding this work in the frame of the project “Inferox” (project…
CCDC 1995182: Experimental Crystal Structure Determination
Related Article: Estefanía Tiburcio, Rossella Greco, Marta Mon, Jordi Ballesteros-Soberanas, Jesús Ferrando-Soria, Miguel López-Haro, Juan Carlos Hernández-Garrido, Judit Oliver-Meseguer, Carlo Marini, Mercedes Boronat, Donatella Armentano, Antonio Leyva-Pérez, Emilio Pardo|2021|J.Am.Chem.Soc.|143|2581|doi:10.1021/jacs.0c12367
CCDC 2107391: Experimental Crystal Structure Determination
Related Article: Rossella Greco, Estefania Tiburcio-Fortes, Antonio Fernandez, Carlo Marini, Alejandro Vidal-Moya, Judit Oliver-Meseguer, Donatella Armentano, Emilio Pardo, Jesús Ferrando-Soria, Antonio Leyva-Pérez|2022|Chem.-Eur.J.|28||doi:10.1002/chem.202103781
CCDC 1995184: Experimental Crystal Structure Determination
Related Article: Estefanía Tiburcio, Rossella Greco, Marta Mon, Jordi Ballesteros-Soberanas, Jesús Ferrando-Soria, Miguel López-Haro, Juan Carlos Hernández-Garrido, Judit Oliver-Meseguer, Carlo Marini, Mercedes Boronat, Donatella Armentano, Antonio Leyva-Pérez, Emilio Pardo|2021|J.Am.Chem.Soc.|143|2581|doi:10.1021/jacs.0c12367
CCDC 1995183: Experimental Crystal Structure Determination
Related Article: Estefanía Tiburcio, Rossella Greco, Marta Mon, Jordi Ballesteros-Soberanas, Jesús Ferrando-Soria, Miguel López-Haro, Juan Carlos Hernández-Garrido, Judit Oliver-Meseguer, Carlo Marini, Mercedes Boronat, Donatella Armentano, Antonio Leyva-Pérez, Emilio Pardo|2021|J.Am.Chem.Soc.|143|2581|doi:10.1021/jacs.0c12367