The MOF-driven synthesis of supported palladium clusters with catalytic activity for carbene-mediated chemistry

• Published in: Nature materials 2017-07, Vol.16 (7), p.760-766
• Main Authors: Fortea-Pérez, Francisco R., Mon, Marta, Ferrando-Soria, Jesús, Boronat, Mercedes, Leyva-Pérez, Antonio, Corma, Avelino, Herrera, Juan Manuel, Osadchii, Dmitrii, Gascon, Jorge, Armentano, Donatella, Pardo, Emilio
• Format: Article
• Language: English
• Subjects: 639/301/299/921; 639/638/298/921; 639/638/77/887; Biomaterials; Catalysis; Catalysts; Catalytic activity; Chemical synthesis; Chemistry; Condensed Matter Physics; Materials Science; Metal clusters; Molecules; Nanotechnology; Optical and Electronic Materials; Oxidation; Palladium
• ISSN: 1476-1122; 1476-4660
• DOI: 10.1038/nmat4910

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 Pd 4 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 Pd 4 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. Mixed-valence clusters of Pd 4 organized within a metal–organic framework exhibit robust catalytic capacities during carbene-mediated chemical reactions.