KIT-5 Structural and Textural Changes in Response to Different Methods of Functionalization with Sulfonic Groups.

In this project, KIT-5 materials were effectively functionalized with sulfonic groups introduced by grafting or the co-condensation method and tested as heterogeneous solid acid catalyst. A co-condensation procedure leading to the stable, -SO3H functionalized KIT-5 materials was successfully established. Moreover, the influence of both synthesis methods on the structural and textural parameters, as well as surface chemistry, morphology, and catalytic activity of -SO3H/KIT-5 materials was thoroughly investigated. The syntheses with 3-mepkaptopropyltrimethoxysilane (MPTMS) acting as a modifying agent resulted in samples in which functional groups were introduced into the structure and/or onto the mesoporous silica surface. The oxidation stage of -SH to -SO3H groups was carried out under mild conditions, using a "green" oxidant (H2O2). The application of different functionalization techniques and the introduction of different amounts of modifying agent allowed for an evaluation of the influence of these parameters on the ordering of the mesoporous structure of KIT-5 materials. The applied methods of assessment of the physicochemical parameters (XRD, low-temperature N2 sorption, TEM) showed that, especially when the co-condensation method was applied, as the number of functional groups increased, the ordering of structure characteristic of KIT-5 decreased. On the other hand, the samples modified by grafting had a stable structure, regardless of the amount of introduced MPTMS. Test reactions carried out on the basis of Friedel-Crafts alkylation process showed that the synthesized materials can be considered promising acid catalysts in heterogeneous catalysis reactions.

Hierarchical Zeolites Containing Vanadium or Tantalum and Their Application in Cyclohexene Epoxidation Reaction.

The aim of this study was the synthesis, characterization, and catalytic application of new hierarchical materials modified with tantalum and vanadium ions. These materials exhibit secondary porosity, thus allowing the reactant molecules to access the active sites of the material while maintaining the acidity and crystallinity of the zeolites. Based on the results, these systems were found to be highly active and selective in the oxidation of cyclohexene. The performance of the catalysts was compared in oxidation processes carried out by conventional and microwave-assisted methods. Microwave-assisted experiments showed that in the presence of a hierarchical FAU zeolite containing Ta, long reaction times could be shortened with increased activity and selectivity under the same residual experimental conditions.