The MOF-driven synthesis of supported palladium clusters with catalytic activity for carbene-mediated chemistry
Francisco R. Fortea-Pérez (Universidad de Valencia (ICMol))
Marta Mon (Universidad de Valencia (ICMol))
Jesús Ferrando-Soria (Universidad de Valencia (ICMol))
Mercedes Boronat (Universitat Politécnica de Valencia)
Antonio Leyva-Pérez (Universitat Politécnica de Valencia)
Avelino Corma (Universitat Politécnica de Valencia)
Juan Manuel Herrera (Universidad de Granada)
Dmitrii Osadchii (TU Delft - ChemE/Catalysis Engineering)
Jorge Gascon (TU Delft - ChemE/Catalysis Engineering)
Donatella Armentano (University of Calabria)
Emilio Pardo (Universidad de Valencia (ICMol))
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Abstract
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 clusters retain their catalytic activity in repeated batch and flow reactions (>20 cycles). Our findings demonstrate how this synthetic approach may now instruct the future design of heterogeneous catalysts with advantageous reaction capabilities for other important processes.