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…
The MOF-driven synthesis of supported palladium clusters with catalytic activity for carbene-mediated chemistry
The development of catalysts able to assist industrially important chemical processes is a topic of high importance. In view of the catalytic capabilities of small metal clusters, research efforts are being focused on the synthesis of novel catalysts bearing such active sites. Here we report a heterogeneous catalyst consisting of Pd4 clusters with mixed-valence 0/+1 oxidation states, stabilized and homogeneously organized within the walls of a metal-organic framework (MOF). The resulting solid catalyst outperforms state-of-the-art metal catalysts in carbene-mediated reactions of diazoacetates, with high yields (>90%) and turnover numbers (up to 100,000). In addition, the MOF-supported Pd4 c…
Synthesis of Densely Packaged, Ultrasmall Pt02Clusters within a Thioether-Functionalized MOF: Catalytic Activity in Industrial Reactions at Low Temperature
The gram-scale synthesis, stabilization, and characterization of well-defined ultrasmall subnanometric catalytic clusters on solids is a challenge. The chemical synthesis and X-ray snapshots of Pt02 clusters, homogenously distributed and densely packaged within the channels of a metal-organic framework, is presented. This hybrid material catalyzes efficiently, and even more importantly from an economic and environmental viewpoint, at low temperature (25 to 140 °C), energetically costly industrial reactions in the gas phase such as HCN production, CO2 methanation, and alkene hydrogenations. These results open the way for the design of precisely defined catalytically active ultrasmall metal c…
Confined Pt-1(1+) Water Clusters in a MOF Catalyze the Low-Temperature Water-Gas Shift Reaction with both CO2 Oxygen Atoms Coming from Water
[EN] The synthesis and reactivity of single metal atoms in a low-valence state bound to just water, rather than to organic ligands or surfaces, is a major experimental challenge. Herein, we show a gram-scale wet synthesis of Pt-1(1+) stabilized in a confined space by a crystallographically well-defined first water sphere, and with a second coordination sphere linked to a metal-organic framework (MOF) through electrostatic and H-bonding interactions. The role of the water cluster is not only isolating and stabilizing the Pt atoms, but also regulating the charge of the metal and the adsorption of reactants. This is shown for the low-temperature water-gas shift reaction (WGSR: CO + H2O CO2 + H…
Partial Reduction and Selective Transfer of Hydrogen Chloride on Catalytic Gold Nanoparticles
© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim HCl in solution accepts electron density from Au NPs and partially reduces at room temperature, as occurs with other simple diatomic molecules, such as O2 and H2. The activation can be run catalytically in the presence of alkynes to give exclusively E-vinyl chlorides, after the regio- and stereoselective transfer of HCl. Based also on this method, vinyl chloride monomer (VCM) can be produced in a milder and greener way than current industrial processes.
A Multisite Molecular Mechanism for Baeyer-Villiger Oxidations on Solid Catalysts Using Environmentally Friendly H2O2 as Oxidant
The molecular mechanism of the Baeyer-Villiger oxidation of cyclohexanone with hydrogen peroxide catalyzed by the Sn-beta zeolite has been investigated by combining molecular mechanics, quantum-chemical calculations, spectroscopic, and kinetic techniques. A theoretical study of the location of Sn in zeolite beta was performed by using atomistic force-field techniques to simulate the local environment of the active site. An interatomic potential for Sn/Si zeolites, which allows the simulation of zeolites containing Sn in a tetrahedral environment, has been developed by fitting it to the experimental properties of quartz and SnO 2 (rutile). The tin active site has been modeled by means of a S…
Selective Introduction of Acid Sites in Different Confined Positions in ZSM-5 and Its Catalytic Implications
Controlling the location of acid sites in zeolites can have a great effect on catalysis. In this work we face the objective of directing the location of Al into the 10R channels of ZSM-5 by taking advantage of the structural preference of B to occupy certain positions at the channel intersections, as suggested by theoretical calculations. The synthesis of B-Al-ZSM-5 zeolites with variable Si/Al and Si/B ratios, followed by B removal in a postsynthesis treatment, produces ZSM-5 samples enriched in Al occupying positions at 10R channels. The location of the acid sites is determined on the basis of the product distribution of 1-hexene cracking as a test reaction. The higher selectivity to prop…
Predicting the activity of single isolated Lewis acid sites in solid catalysts.
An experimental study of the activity of Ti-, Zr- and Sn-beta catalysts in different types of oxidation reactions is combined with a quantum-chemical analysis of the electronic properties of the active sites and the adsorbed reactants. The differences observed in the catalytic behaviour of the three materials are explained in terms of the molecular orbital distribution of each system. The intrinsic Lewis acid strength of the isolated active site, the degree of back-donation from the catalyst to the empty orbitals of the organic reactant and the net atomic charges on selected atoms are proposed as predictors of reactivity.
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 1587822: Experimental Crystal Structure Determination
Related Article: Marta Mon, Miguel A. Rivero-Crespo, Jesffls Ferrando-Soria, Alejandro Vidal-Moya, Mercedes Boronat, Antonio Leyva-Pérez, Avelino Corma, Juan C. Hernandez-Garrido, Miguel Lopez-Haro, José J. Calvino, Giulio Ragazzon, Alberto Credi, Donatella Armentano, Emilio Pardo|2018|Angew.Chem.,Int.Ed.|57|6186|doi:10.1002/anie.201801957
CSD 1409698: Experimental Crystal Structure Determination
Related Article: Marta Mon, Miguel A. Rivero-Crespo, Jesffls Ferrando-Soria, Alejandro Vidal-Moya, Mercedes Boronat, Antonio Leyva-Pérez, Avelino Corma, Juan C. Hernandez-Garrido, Miguel Lopez-Haro, José J. Calvino, Giulio Ragazzon, Alberto Credi, Donatella Armentano, Emilio Pardo|2018|Angew.Chem.,Int.Ed.|57|6186|doi:10.1002/anie.201801957
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
CCDC 1841391: Experimental Crystal Structure Determination
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CCDC 1517224: Experimental Crystal Structure Determination
Related Article: Francisco R. Fortea-Pérez, Marta Mon, Jesús Ferrando-Soria, Mercedes Boronat, Antonio Leyva-Pérez, Avelino Corma, Juan Manuel Herrera, Dmitrii Osadchii, Jorge Gascon, Donatella Armentano and Emilio Pardo|2017|Nat.Mater|16|760|doi:10.1038/nmat4910
CCDC 1587821: Experimental Crystal Structure Determination
Related Article: Marta Mon, Miguel A. Rivero-Crespo, Jesffls Ferrando-Soria, Alejandro Vidal-Moya, Mercedes Boronat, Antonio Leyva-Pérez, Avelino Corma, Juan C. Hernandez-Garrido, Miguel Lopez-Haro, José J. Calvino, Giulio Ragazzon, Alberto Credi, Donatella Armentano, Emilio Pardo|2018|Angew.Chem.,Int.Ed.|57|6186|doi:10.1002/anie.201801957
CCDC 1841392: Experimental Crystal Structure Determination
Related Article: Miguel A. Rivero-Crespo, Marta Mon, Jesús Ferrando-Soria, Christian W. Lopes, Mercedes Boronat, Antonio Leyva-Pérez, Avelino Corma, Juan C. Hernández-Garrido, Miguel López-Haro, Jose J. Calvino, Enrique V. Ramos-Fernandez, Donatella Armentano, Emilio Pardo|2018|Angew.Chem.,Int.Ed.|57|17094|doi:10.1002/anie.201810251
CCDC 1517225: Experimental Crystal Structure Determination
Related Article: Francisco R. Fortea-Pérez, Marta Mon, Jesús Ferrando-Soria, Mercedes Boronat, Antonio Leyva-Pérez, Avelino Corma, Juan Manuel Herrera, Dmitrii Osadchii, Jorge Gascon, Donatella Armentano and Emilio Pardo|2017|Nat.Mater|16|760|doi:10.1038/nmat4910