Synergistic Hydrogenation over Palladium through the Assembly of MIL-101(Fe) MOF over Palladium Nanocubes.

Enhancing catalytic performance of metal nanoparticles is highly sought for many industrial catalytic processes. In this regard, assembly of crystalline porous super-tunable metal-organic frameworks (MOFs) around preformed metal nanoparticles is an attractive prospect as this strongly influences the activity of the entire nanoparticle surface. Herein, we assembled a MlL-101(Fe) MOF onto the Pd nanocubes and evaluated the catalytic properties of the hybrid material for the hydrogenation of the α,β-unsaturated carbonyl compounds cinnamaldehyde, crotonaldehyde, and β-ionone. Owing to the synergestic effects originating from the Lewis acid sites present on MOF and Pd active sites, striking improvements in the activities and selectivities were observed for the Pd⊂MIL-101(Fe) hybrid material. The turnover frequency (TOF) values increased up to roughly 20 fold and in all three studied substrates, C=C was preferentially hydrogenated compared to C=O. Furthermore, the Pd⊂MIL-101(Fe) catalyst was readily reusable and highly stable.