The economic and environmental benefits of heterogeneous catalysts and their high potential to be employed in industrial processes and flow chemistry justify the continuous interest to develop new, efficient and selective systems.The robust metal-organic framework MIL-101 constitutes an excellent support for the active catalytic species. Furthermore, post-synthetic modifications can be applied for the insertion of new chemical functionalities into the backbone of the MOF (Scheme 1). [1,2] This strategy allows us to accurately tailor the inner-surface of the pores to better accommodate the catalyst, so that no leaching occurs.Scheme 1: Post-synthetic modification of Cr-MIL-101We herein present the first extensive study of the applicability but also the limitations of this support. Further we compare different catalyst loadings to find an optimal balance between the active species and the space that needs to remain accessible for substrates. The thorough work performed for tuning the material's pores allowed us to achieve an unprecedented low leaching of palladium. Advanced spectroscopic and microscopic methods were used for a detailed characterization.This heterogeneous catalyst proved to be extremely active in a range of organic reactions, including the Suzuki coupling of challenging substrates in water, at room temperature and the aerobic oxidation of alcohols in mild conditions. These properties are easily maintained after recycling.References:G. Ferey, et al., Science, 2005  , 309, 2040-2042.N. Stock, et al., Chem. Commun., 2011  , 47, 2838-2840.

Heterogeneous catalysis with immobilized palladium nanoparticles on metal-organic frameworks

246th National Meeting (2013)

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