Hydroformylation of olefins over rhodium supported metal-organic framework catalysts of different structure

Abstract

The metal-organic framework IRMOF-3 has been synthesized and functionalized with supported rhodium species. The samples have been characterized by XRD, FTIR, SEM, TEM, XPS, AAS, and nitrogen sorption measurements. It is found that originally precipitated big particles consist of hierarchically structured agglomerated nanocrystals of ca. 10–15nm size. The big particles contain a combined macro–meso–micro pore system allowing easy access to the catalytic sites. The Rh@IRMOF-3 supported catalyst has been catalytic tested in the hydroformylation of olefins to the corresponding aldehydes. Double bond shift isomerization has been observed as side reaction. n-Alkenes-1 of different chain lengths and bulky or less flexible olefins as cyclohexene, 2,2,4-trimethylpentene, and hexadiene-1,5 have been studied. The Rh@IRMOF-3 catalyst shows high activity and selectivity to n-aldehydes in the hydroformylation of linear alkene-1. The comparison of catalytic data obtained with the hydroformylation of n-hexene-1 over the different rhodium loaded MOFs as MOF-5, MIL-77, and MIL-101 show a significant influence of the MOF-structure on the catalytic properties.