6 research outputs found
Post-synthetic Modification of DUT-5-based Metal Organic Frameworks for the Generation of Single-site Catalysts and their Application in Selective Epoxidation Reactions
New singleâsite catalysts based on mixedâlinker metalâorganic frameworks with DUTâ5 structure, which contain immobilized Co2+, Mn2+ and Mn3+ complexes, have successfully been synthesized via postâsynthetic modification. 2,2ââBipyridineâ5,5ââdicarboxylate linkers were directly metalated, while 2âaminoâ4,4ââbiphenyldicarboxylate linkers were postâsynthetically modified by their conversion to Schiffâbase ligands and a subsequent immobilization of the metal complexes. The resulting materials were used as catalysts in the selective epoxidation of transâstilbene and the activities and selectivities of the different catalysts were compared. The influence of various reaction parameters on conversion, yield and selectivity were investigated. Very low catalyst amounts of 0.02â
molâ% were sufficient to obtain a high conversion of transâstilbene using molecular oxygen from air as the oxidant. For cobaltâcontaining MOF catalysts, conversions up to 90â% were observed and, thus, they were more active than their manganeseâcontaining counterparts. Recycling experiments and hot filtration tests proved that the reactions were mainly catalyzed via heterogeneous pathways