Synthesis and catalytic activity of ZIF-8 and doped-ZIF-8 crystals: stability and cytotoxicity evaluation

Metal organic frameworks (MOFs) have gained considerable attention as heterogeneous catalytic systems and also have been studied in the area of separation, gas storage, controlled release or as drug delivery systems. According to their complex structure formed by metal centers coordinated with polydentate linkers, MOFs expose abundance of Lewis and/or Brönsted acid-base sites that are crucial for the materials catalytic activity and selectivity towards specific reactions. Moreover, these materials have many other attractive properties, including a large surface area, a low density and a high porosity. In this work, we focused on the zeolithic imidazolate framework (ZIF-8) material – a MOF exhibiting high porosity and stability and which can also be used as a template for further functionalization and modification. Firstly, we focused on the preparation of ZIF-8 crystals and ZIF-8 heterostructures with properties adapted to the desired application, and then shaping of the catalyst to obtain the best form of material for industrial scale-up utilization. By varying Zn2+ precursors used for the synthesis, we demonstrated that the properties (size, porosity,…) of ZIF-8 crystals can be controlled and tuned depending on the applications. These ZIF-8 crystals were successfully applied as heterogeneous catalysts in Knoevenagel and Friedländer reactions. Next, we developed protocols for the synthesis of Cu2+-doped ZIF-8 crystals. The use of these crystals could be extended to Cu-mediated reactions, like the Combes condensation and the Huisgen cycloaddition. We evaluated recyclability and we showed that the nanomaterials could be reused up to ten times without any loss of catalytic activity. Moreover, we functionalized ZIF-8 crystals with magnetic Fe3O4 nanoparticles. The hybrid Fe3O4@ZIF-8 heterostructures could be easily recovered by magnetic separation after catalytic experiments. To show multiple benefits originating from the ZIF-8 structure and properties, we also used this material for the conversion of CO2 into cyclic carbonates using a Parr reactor. As the reaction could be scale-up at the industrial level, we shaped the powder in the form of pellets and use it under the same conditions. In the last chapter, we evaluated the toxicity and the stability in biological media of ZIF-8, Cu- and Fe-doped ZIF-8 particles using A549 alveolar cells, IHK skin cells as models and in vitro ingestion under fed conditions. These models were chosen according to the most probable first contact entering gates for nanoparticles inside human body, skin, lungs and digestive tract. Outcomes from these preliminary studies motivated us to conduct extended stability tests of the particles in different media. We showed that the particles are altered by pH changes and medium complexity