Bimetallic MnZn-MOF-74 with enhanced percentage of MnIII: Efficiently catalytic activity for direct oxidative carboxylation of olefins to cyclic carbonates under mild and solvent-free condition

Multi-functional MOF catalyst with oxidative- and acid- centers showed potential in olefins oxidative carboxylation to cyclic carbonates directly. In this work, a series of bimetallic MnZn-MOF-74 with different molar ratios of Mn and Zn were synthesized successfully through a one-pot facile method. Thoroughly characterization indicated that the existence of Zn regulated the valance state distribution of Mn in the obtained MnZn-MOF-74. Mn99.3Zn0.7-MOF-74 with the highest ratio of MnIII (61.3 %) performed the most efficient activity for olefin direct tandem oxidative carboxylation reaction using aqueous tert-butyl hydroperoxide oxidant under solvent-free condition of 90 degrees C, 1.0 MPa CO2 and 4 h. Mn99.3Zn0.7-MOF-74 also showed satisfactory versatility and recyclability. Based on the experiments, a feasible mechanism was presented. Thanks to the high ratio of active MnIII as main oxidative center, the coordination unsaturated bimetal Mn and Zn as Lewis-acid sites, O2- of metal - O as Lewis-base sites and combined effect with Bu4NBr cocatalyst, Mn99.3Zn0.7-MOF-74 presented efficient performance for the direct synthesis of cyclic carbonates from olefins. The metal Zn in MOF can regulate the valance state distribution of Mn and result in efficient catalytic property, presenting a potential avenue for direct oxidative carboxylation reaction of olefins to cyclic carbonates synthesis.