Selective hydroformylation of olefins over the rhodium supported large porous metal–organic framework MIL-101

• Extra-large porous Rh@MIL-101 has been prepared with an improved procedure.
• The catalyst was tested in the hydroformylation of different olefins.
• High activity and selectivity to n-aldehydes are achieved.
• Large olefins and especially internal alkenes are very slowly converted.
• Rh proposed to be located at less accessible supertetrahedral units of the walls.

Highly porous and crystalline metal–organic framework MIL-101 has been synthesized and used for the preparation of rhodium supported catalyst. Acetylacetonato(1,5-cyclooctadiene)rhodium(I) has been used as catalyst precursor. The material has been characterized by XRD, XPS, SAXS, FTIR, SEM, TEM, AAS, and nitrogen adsorption. The catalytic properties of Rh@MIL-101 have been investigated in the hydroformylation of olefins with different structure and chain length to the corresponding aldehydes. High conversion and selectivity to n-aldehydes have been achieved in the hydroformylation of n-alk-1-enes. The obtained results show that the rhodium species are highly dispersed and preferentially located at internal and less accessible sites at the supertetrahedral units.

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