Increasing the ion-exchange capacity of MFI zeolites by introducing Zn to aluminosilicate frameworks

MFI zeolites exchanged with various cations have gained a great deal of attention as catalysts. Increase in the ion-exchange capacity of zeolites can improve their catalytic properties by introducing more active sites; however, the ion-exchange capacity of MFI zeolites is limited by maximum aluminum content in the structure. To improve the ion-exchange capability of the MFI zeolites beyond the upper limit of the aluminosilicate MFI zeolites, we propose herein an approach to incorporate Zn(ii) in the zeolitic framework, because Zn in the framework sites generates two negative charges per atom. Using zincoaluminosilicate gels prepared via co-precipitation, organic-free synthesis of zincoaluminosilicate MFI zeolites was achieved. The obtained zincoaluminosilicate MFI zeolites had high Zn contents comparable to those in the initial zincoaluminosilicate gels with both Zn and Al in the zeolite framework. In contrast, the use of conventional sources of Si, Al, and Zn resulted in zeolites with extra-framework zinc oxide species. The obtained Zn-substituted MFI zeolites were shown to possess higher ion-exchange capacity compared to aluminosilicate MFI zeolites. It was also revealed that the zincoaluminosilicate MFI zeolites have high affinity for the divalent cation compared to the aluminosilicate analog, likely due to the two negative charges in close proximity. Because of these higher ion-exchange efficiencies, especially for divalent cations, the obtained zincoaluminosilicate MFI zeolites are expected to be efficient platforms for several important catalytic reactions.