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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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Labile elementosilicates as intermediates for design of novel materials
Yue, Qiudi ; Opanasenko, Maksym (advisor) ; Hronec, Mlan (referee) ; Zima, Vítězslav (referee)
Zeolites are crystalline microporous materials with three-dimensional frameworks built from corner-sharing TO4 tetrahedra. Traditionally, zeolites are defined as aluminosilicates (T = Si and Al). Nowadays, the skeleton atoms have been expanded to other tri-/tetra-valent elements, including B, Ga, Ge, Ti, etc., due to the chemical flexibility of zeolites. Resulting materials are termed as elementosilicates for respective element-containing zeolites. Such materials exhibit fascinating properties due to the different nature of elements in the framework, e.g. structural flexibility and tunable acidity. Taking advantage of the unique properties of elementosilicate zeolites, their applications as the starting solids for the synthesis of new materials and as adsorbents for gas separation have made great progress. However, the complexity of the factors affecting the zeolite synthesis limits the possibility to control the key parameters of zeolites formation, e.g. crystallization mechanism, crystal growth rate, and phase selectivity. From the another side, for particular zeolite systems being perspective for gas separation, correlation between the chemical composition of designed structures and their adsorption performance is elusive. Considering the above statements, this thesis was focused on the design...
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Metal nanoparticles in zeolites
Zhang, Yuyan ; Čejka, Jiří (advisor) ; Zima, Vítězslav (referee) ; Kubička, David (referee)
Zeolites with encapsulated metal nanoparticles have attracted a wide attention in heterogeneous catalysis due to their high catalytic activity, selectivity, and stability. The PhD thesis was focused on design and synthesis of metal@zeolite catalysts with small and uniformly distributed metal nanoparticles. The main interests were encapsulation of metal nanoparticles into zeolites by co-crystallization strategy and 2-dimensional to 3-dimensional zeolite transformation approach. The PhD work was performed at the Department of Synthesis and Catalysis at J. Heyrovský Institute of Physical Chemistry and Department of Physical and Macromolecular Chemistry, Faculty of Science at Charles University under the supervision of Prof. Jiří Čejka. Zeolites are inorganic crystalline aluminosilicates with microporous framework structures. The micropores of zeolites provide the ideal microenvironment to accommodate metal nanoparticles. During metal nanoparticles formation in zeolite micropores, they can be limited by a rigid framework, preventing the aggregation and leaching of metal during the reaction process. Furthermore, the diameters of zeolite micropores are usually in the range of 0.3-1.5 nm, which can be used to discriminate molecules depending on their size and shape, thus endowing the metal@zeolite...
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Design and catalytic application of novel nanostructured materials
Zhou, Yong ; Opanasenko, Maksym (advisor) ; Bulánek, Roman (referee) ; Zima, Vítězslav (referee)
Zeolites are crystalline aluminosilicates and environmentally friendly solid acid catalysts thanks to their non-toxicity, large surface area, excellent (hydro)thermal stability, and tunable acidity. Traditionally, zeolite catalysts are applied in industrial processes related to petrochemistry, but several studies have recently shown their high potential in fine chemicals production and volatile organic compounds (VOCs) elimination. Advanced materials based on newly developed layered and nanosized zeolites have exhibited further fascinating properties, e.g., a short diffusion pathway, tunable structure and morphology. However, the limited correlation between key parameters of zeolite synthesis and their properties (structural, textural, acidic) and catalytic performance, especially for new layered and nanosized zeolites, hinders the development and application of zeolite catalysts. Considering the above, this thesis focused on the preparation of several sets of specific zeolite catalysts to gain further insights into the relationship between key properties of zeolites (structure, morphology, chemical composition, accessibility to acid sites or other functional groups, and organization of layers, among others) and their performance as catalysts, supports for other active phases or nanosized...
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Design of zeolite materials with tailored interlayer structure and tunable textural properties
Kasneryk, Valeryia ; Opanasenko, Maksym (advisor) ; Zima, Vítězslav (referee) ; Shvets, Oleksiy (referee)
Germanosilicate zeolites attracted a lot of attention during the last decade. The reason for such interest is related to the unique structural properties of germanosilicates, which include zeolites of UTL, UOV, ITH, IWR, IWW, and CIT-13 types. The frameworks of these materials can be described as Si-rich layers connected by double four ring (D4R) units preferentially occupied by Ge atoms. Hydrolytic instability of Ge-O bonds in mentioned frameworks compared with Si-O bonds in conventional zeolites gives the opportunity for controllable chemically selective transformation of the germanosilicate frameworks towards novel types of zeolites including their 2D analogues. This PhD thesis focuses on modification of the structure and textural properties of germanosilicates using different ways of post-synthesis treatment: the ADOR (Assembly - Disassembly - Organization - Reassembly) transformation and post-synthesis degermanation and alumination. Presented work was carried out in the Department of Synthesis and Catalysis at J. Heyrovský Institute of Physical Chemistry in Prague under the supervision of Dr. Maksym Opanasenko and advising of Prof. Jiři Čejka. First way of post-synthesis treatment applied in this work was the recently developed method of zeolite synthesis - the ADOR transformation....
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Layered Transition Metal Hydroxides: Delamination and Properties
Hyklová, Barbora ; Lang, Kamil (advisor) ; Zima, Vítězslav (referee) ; Bujdák, Juraj (referee)
Charles University Faculty of Science Study programme: Inorganic Chemistry Mgr. Barbora Hyklová Layered Transition Metal Hydroxides: Delamination and Properties Extended abstract Supervisor: Ing. Kamil Lang CSc., DSc. Supervisor-Consultant: RNDr. Jan Demel PhD. Prague, 2017 Layered transition-metal hydroxides have attracted increasing attention as promising active electrode materials for electrochemical energy storage and conversion device due to facile preparation and modification, good tunability, high capacitance capability, fast reversible redox reactions, and cost effectiveness. Many reported hierarchical architectures based on nickel and cobalt hydroxides are composed of bulky nanoplatelet-like aggregates; however, the nanomorphology and behavior of the separated hydroxide nanosheets is much less known. Figure 1. Scheme of layered nickel or cobalt hydroxide delamination and subsequent restacking on conductive HOPG support. In this respect, the dissertation thesis reports characterization and electrochemical performance of nickel, nickel-cobalt, and cobalt hydroxide nanosheets, synthesized by an economical and environmentally friendly method based on delamination of corresponding layered hydroxides in water (Figure 1). For this purpose, lactate and nitrate layered hydroxides were prepared by two...
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Chemistry of the Interlamellar Space of Two-dimensional Zeolites
Mazur, Michal ; Čejka, Jiří (advisor) ; Zima, Vítězslav (referee) ; Hronec, Mlan (referee)
The presented PhD thesis is focused on the synthesis, characterization, and modifications of zeolites and zeolitic materials. The main interests are two-dimensional (2D) zeolites and modification of their interlamellar space. Presented work was performed at the Department of Synthesis and Catalysis at J. Heyrovský Institute of Physical Chemistry in Prague, Czech Republic under the supervision of Prof. Jiří Čejka. Zeolites are inorganic crystalline solids with a microporous framework structure. They are widely used as catalysts, sorbents, and ion-exchangers. Conventional zeolites have been recognized as three-dimensional (3D) tetrahedrally-connected frameworks. However, some of them are also known to exist in various layered forms (2D zeolites). Recently, the transformation of 3D germanosilicate UTL into layers (IPC-1P) has started a new branch in 2D zeolites chemistry. This chemically selective degradation of UTL framework was performed via acid hydrolysis. In the structure of this germanosilicate, Ge atoms are preferentially located in specific building units, double-four-rings (D4R), which connect dense silica layers. Modifications of the layered precursor IPC-1P led to discovery of the two novel 3D zeolites: IPC-4 (PCR) and IPC-2 (OKO). This novel approach in the zeolite synthesis, called ADOR...
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16th International Symposium on Intercalation Compound - ISIC16. Abstracts Book
Zima, Vítězslav ; Kavan, Ladislav ; Čejka, Jiří ; Lang, Kamil ; Vlček, Milan ; Beneš, L. ; Svoboda, Jan ; Melánová, Klára ; Frumarová, Božena ; Knotek, P. ; Jůza, Josef ; Látalová, Petra
The topic of the papers published in this proceedings is chemistry, properties and applications of intercalation compounds and related materials.
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Organofosfonáty kovů a jejich interkalační sloučeniny jako anorganicko-organické hybridní materiály a nanomateriály
Zima, Vítězslav ; Svoboda, Jan ; Melánová, Klára ; Beneš, L.
We prepared several new phenylphosphonates and 4-carboxyphenylphosphonates of alkaline earth metals and copper and characterized them by powder X-ray diffraction, thermogravimetric analysis, energy-dispersive X-ray analysis, elemental analysis and infrared spectroscopy. For four of these compounds, their structure was determined from their powder X-ray diffraction patterns using an ab initio FOX program. The prepared alkaline-earth phenylphosphonates with general formula MeC6H5PO3yH2O (Me = Ca, Sr, Ba) were found to be suitable hosts for intercalation reactions.
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