Une nouvelle approche de synthèse a été développée pour non seulement contrôler la morphologie, la taille et la texture de particules de silice mais aussi incorporer une ou plusieurs fonctionnalités à la surface interne de leurs pores. La morphologie sphérique, la monodispersité des particules, la porosité radiale, la dispersion et l'accessibilité des fonctionnalités ainsi que leur taux d'incorporation constituent les propriétés et les paramètres physico-chimiques privilégiés dans notre approche qui est basée sur la méthode de Stöber modifiée et la fonctionnalisation in-situ. Deux différentes applications ont été retenues pour étudier la quintessence de cette approche. La première consiste à incorporer des espèces métalliques (Al et Cu par exemple) dans les sphères de silice afin de les rendre fonctionnelles pour des applications catalytiques en phase liquide; et la deuxième consiste à greffer à la surface des particules des nanomachines sensibles permettant de contrôler le relargage des molécules actives pour des applications thérapeutiques. Dans les deux cas d'application, des performances optimales sont attendues. / A novel approach of synthesis has been developed in order to control simultaneously the morphology, size and textural parameters of silica particles, as well as to incorporate one or more functional groups in the pore walls. In this approach, based on the modified Stöber method and in-situ functionalization, emphasis is put on the spherical morphology, the particle monodispersity, the radially disposed porous structure, and the appropriate dispersion and accessibility of surface functional groups. Two potential applications have been selected so as to verify the feasibility of the approach. In view of materials use for heterogenous catalysis in the liquid phase, the monodisperses mesoporous silica spheres were derivatized with metallic species (e.g., Al and Cu) by direct incorporation in the synthesis stage. The second type of applications concerned the use of silica spheres as sensitive nanomachines for the controlled drug release and required grafting of appropriate organic molecules onto the silica surface.

Preparation of hierarchical zeolites for fine chemical synthesis Author: Bc. Ondřej Veselý Supervisor: Mgr. Pavla Eliášová, Ph.D. Prague, 2019 Abstract (in english): The thesis is focused on synthesis of hierarchical (micro-mesoporous) zeolites by several different methods and their application in catalytic reactions. Performance of hierarchical materials prepared by different approaches has been investigated, as well as the effect of framework topology and type of acidity on the outcome of the reactions. The work was elaborated in the Department of Physical and Macromolecular Chemistry of Charles University under the supervision of Mgr. Pavla Eliášová, Ph. D. The work is divided into three parts. In the first part several methods of preparation of hierarchical zeolites have been investigated and compared in catalytic reactions. Desilication, selective removal of silicon from the framework, is a post-synthetic method that can be used to introduce additional mesoporosity into a zeolite. The process leads to formation of mesopores by introducing defects into the zeolite structure. The resulting mesopore size is very broad. To partially control the pore size, alkylammonium cations may be added to the solution to protect the crystal surface. The desilication was performed on MTW zeolite which contains...

The object of this thesis is to get a deeper understanding of the role of modulator agents in the synthesis of Zr- and Hf-based metal-organic frameworks (MOFs) and their impact on framework properties, such as textural properties, stability, hydrophobicity, and catalytic activity. For this purpose, MOFs are investigated that are built up by the commercially available linker 2,5-thiophenedicarboxylate and the Zr6(µ3-O)4(µ3-OH)412+ cluster. With proper choice of the modulator a new structure, namely DUT-126 (DUT = Dresden University of Technology), could be presented in the course of this work, besides the already known polymorphs of DUT-67, DUT-68 and DUT-69. Furthermore, DUT-67 is chosen as a model structure to functionalise the metal cluster of the framework by exchanging the modulator post-synthetically with hydrophobic fluorinated monocarboxylic acids. With the introduction of these fluorinated molecules, the surface polarities and the stability against water removal can be tuned. In addition, the metal clusters of DUT-67 were modified with a complete removal of the pristine modulator molecules by means of an acidic treatment in order to generate open metal sites that can function as Lewis acid sites. The suitability of DUT-67 and its acid treated analogues as heterogenous catalyst was tested on the Meerwein-Ponndorf-Verley reduction of cyclohexanone. Furthermore, the UiO-67 analogue DUT-122, which contains the luminescent linker 9-fluorenone-2,7-dicarboxylate, was tested as sensor material to detect solvent vapours. It could be shown that DUT-122 is sensitive to various solvent vapours, which induce photoluminescent shifts and intensity changes of the fluorescence emission profile depending on the polarity and the functionality of the respective solvent.

The object of this thesis is to get a deeper understanding of the role of modulator agents in the synthesis of Zr- and Hf-based metal-organic frameworks (MOFs) and their impact on framework properties, such as textural properties, stability, hydrophobicity, and catalytic activity. For this purpose, MOFs are investigated that are built up by the commercially available linker 2,5-thiophenedicarboxylate and the Zr6(µ3-O)4(µ3-OH)412+ cluster. With proper choice of the modulator a new structure, namely DUT-126 (DUT = Dresden University of Technology), could be presented in the course of this work, besides the already known polymorphs of DUT-67, DUT-68 and DUT-69. Furthermore, DUT-67 is chosen as a model structure to functionalise the metal cluster of the framework by exchanging the modulator post-synthetically with hydrophobic fluorinated monocarboxylic acids. With the introduction of these fluorinated molecules, the surface polarities and the stability against water removal can be tuned. In addition, the metal clusters of DUT-67 were modified with a complete removal of the pristine modulator molecules by means of an acidic treatment in order to generate open metal sites that can function as Lewis acid sites. The suitability of DUT-67 and its acid treated analogues as heterogenous catalyst was tested on the Meerwein-Ponndorf-Verley reduction of cyclohexanone. Furthermore, the UiO-67 analogue DUT-122, which contains the luminescent linker 9-fluorenone-2,7-dicarboxylate, was tested as sensor material to detect solvent vapours. It could be shown that DUT-122 is sensitive to various solvent vapours, which induce photoluminescent shifts and intensity changes of the fluorescence emission profile depending on the polarity and the functionality of the respective solvent.