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Synthesis of novel zeolite materials and their application in catalysis
Veselý, Ondřej ; Přech, Jan (advisor) ; Zima, Vítězslav (referee) ; Hronec, Mlan (referee)
Zeolites are crystalline microporous tectosilicates with acidic properties. The pore sizes of molecular dimensions restrict molecules from entering/exiting the pores based on the molecule size and geometry, or formation of certain (bulky) transition states within the pores. Accordingly, zeolites have become vital industrial catalysts, adsorbents and ion-exchangers. Zeolites are commonly synthesised by hydrothermal crystallization. However, this method provides only limited control over their crystal structure, morphology, or location of active sites within the framework. Some of these limitations can be overcome using an alternative synthetic method; the Assembly-Disassembly-Organisation- Reassembly (ADOR). The ADOR transforms a parent (germanosilicate) zeolite into a layered precursor and subsequently uses the layers as building blocks for a new zeolite framework. We aimed to develop methodology to control the crystal morphology of germanosilicate zeolite UTL (Assembly), determine the mechanism of the UTL hydrolysis (Disassembly), and to reconstruct the parent UTL zeolite from the ICP-1P layered material (Organisation and Reassembly) since the traditional ADOR yields zeolites of smaller channel size but the parent UTL. We found the UTL crystal morphology progressively varies the Si/Ge molar ratio...
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Influence of bases on heterogeneous Lewis acid catalyzed hydrogen transfer reactions
Veselá, Klára ; Přech, Jan (advisor) ; Bulánek, Roman (referee)
Heterogeneous Lewis acid zeolites catalyzed Meerwein-Ponndorf-Verley (MPV) reduction (transfer hydrogenation), where ketones and aldehydes are reduced to the corresponding alcohols. The hydrogen is taken from a secondary alcohol. These Lewis acid zeolite catalysts have a great advantage over homogenous catalysts as they are well separable from the reaction mixture and recyclable. Lewis acid zeolites are materials that contain incorporated tin or zirconium species, which act as Lewis acid sites. MPV reduction of citronellal provides citronellol as a product. However, the reaction of citronellal with 2- propanol also proceeds via a parallel reaction pathway providing isopulegol as the major product. Addition of pyridine (an organic base) to the reaction mixture switches the selectivity of the reaction, i.e., citronellol becomes the main product of the cited citronellal reaction with 2-propanol. It was investigated whether this phenomenon would also be observed for reactions with the addition of different bases. To answer these questions, Sn-BEA and Zr-BEA were prepared by hydrothermal synthesis. Impreg-Zr-BEA and impreg-Sn-BEA were prepared by postsynthesis metal incorporation. In addition, highly porous 2D Self-pillared pentasil zeolites containing tin and zirconium were hydrothermally synthesized....
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Aplications of hydrogenation catalysts prepared by reductive demetalation of zeolites
Kurucová, Svetlana ; Přech, Jan (advisor) ; Vyskočilová, Eliška (referee)
Hydrogenation reactions belong to the most important reactions in the chemical industry. They are needed for crude oil processing, production of pharmaceutical, polymers, chemical specialties, etc. Supported noble metal catalysts are commonly used industrial catalysts due to their high activity and selectivity. However, the high cost of production and recovery of noble metal catalysts is one of the disadvantages of their use. The application of transition metal catalysts containing Cu, Fe or Zn presents a more environmentally friendly alternative to currently used catalysts. In this work, we studied the catalytic activity of metal@zeolite composite catalysts containing CuFe and CuZn bimetallic nanoparticles, prepared by reductive demetallation in hydrogenation of -NO2, -C≡C-, -C=C- and -C=O groups. Reductive demetallation is a novel method for the synthesis of bimetallic nanoparticles encapsulated inside zeolite pores. The catalytic activity of the metal@zeolite composites prepared by reductive demetallation was compared with analogues synthesised by impregnation and ion exchange in the hydrogenation of p-nitrotoluene, 3-ethynylanisole and cinnamaldehyde. Metal@zeolite catalysts synthesised by reductive demetallation were active in the hydrogenation of all the cited groups: -NO2, -C≡C-, -C=C- and...
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Preparation of hierarchical zeolites for fine chemical synthesis
Veselý, Ondřej ; Eliášová, Pavla (advisor) ; Přech, Jan (referee)
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...
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Heterogeneous catalysis of terpenoid redox reactions
Kurucová, Svetlana ; Přech, Jan (advisor) ; Bulánek, Roman (referee)
Heterogeneous catalysts for Meerwein-Ponndorf-Verley (MPV) reduction of ketones and aldehydes are investigated due to issues connected with water sensitivity and separation problems of homogeneous catalysts. During MPV reduction, a hydrogen atom is transferred from the sacrificial alcohol onto the carbonyl group of the ketone/aldehyde forming corresponding alcohol. Tin and zirconium containing zeolites are active catalysts in this hydrogen transfer reaction. However, when using conventional 3D zeolites in the reduction of bulky molecules, e.g., terpenoid compounds, problems with active site accessibility for these bulky reactants may arise. The use of 2D pillared zeolites may represent a solution to the diffusion problem. Silica metal-oxide pillars increase the distance between individual layers of a 2D (lamellar) zeolite and thus improve the active site accessibility. 2D catalysts were prepared by pillaring a parent lamellar pure-Si MFI with a mixture of tetraethyl orthosilicate and Zr (IV) isopropoxide or Sn (IV) isopropoxide, while conventional 3D zeolites were synthesised hydrothermally. The activity of Sn and Zr containing pillared catalysts was compared with the activity of the 3D MFI and beta zeolites in MPV reduction of furfural and citronellal. The 2D zeolites, however, did not facilitate...
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Preparation of hierarchical zeolites for fine chemical synthesis
Veselý, Ondřej ; Eliášová, Pavla (advisor) ; Přech, Jan (referee)
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...
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Synthesis and Post-synthesis Modification of Novel 2-Dimensional Zeolites
Přech, Jan ; Čejka, Jiří (advisor) ; Bulánek, Roman (referee) ; Hronec, Mlan (referee)
Development of sustainable and environmentally friendly chemical processes is of vital importance nowadays. Although there is a palette of different synthetic methods for the formation of epoxides, sulphoxides and sulphones, from both economic and environmental points of view, a direct oxidation with a simple oxidant is highly appreciated. The main goals of the thesis were design and synthesis of novel titanium containing zeolitic materials with the ability to catalyse selective oxidation of sterically demanding organic compounds, particularly epoxidation of cyclic olefins and terpenes and oxidation of bulky thioethers to corresponding sulphoxides and sulphones with hydrogen peroxide as the oxidant. Two novel extra-large pore titanosilicates were prepared by means of hydrothermal synthesis (Ti-CFI, Ti-UTL), three large-pore titanosilicates (Ti-CON, Ti-AFI, Ti-IFR) were prepared using two step deboronation - liquid phase titanium impregnation procedure and two groups of lamellar materials were prepared. One group was based on modified nanosheet TS-1; the other was prepared from Ti-IPC- 1P lamellar precursor, which was prepared by means of top-down transformation of Ti-UTL. Last but not least, the Ti-UTL was transformed into new titanosilicates Ti-IPC-2 (OKO structure) and Ti-IPC-4 (PCR structure) by...
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