0000000001317259
AUTHOR
Juan C. Hernández-garrido
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…
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…
CCDC 1841391: 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 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