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Dynamic Processes in Porous Nanomaterials: Adsorption and Diffusion
Trachta, Michal ; Bludský, Ota (advisor) ; Heard, Christopher James (referee) ; Čičmanec, Pavel (referee)
Dynamical processes in porous nanomaterials (adsorption, diffusion, separation) play a significant role in many industrial applications. Modeling of these applications theoretically provides atomistic details of adsorption and diffusion phenomena - information that is often difficult to obtain using contemporary experimental methods. Theory may thus provide a deeper insight into these processes, e.g., explaining the mechanisms and assisting in the search for new materials suited for a specific application through material screening. In this work, the dynamical processes in porous materials were investigated by means of force field and ab initio modeling. On a set of relevant simulation data, two particular problems related to the modeling of such processes are thoroughly addressed: (i) the sensitivity of the results to material geometry, and (ii) the accuracy of the potential energy surface description. Regarding the structure description, the reliability of theoretically-predicted structures is still limited, despite the significant increase in computational power and algorithm development. The drawbacks of individual methods are identified; even state-of-the-art density functional theory approaches suffer from inaccuracies, e.g., due to an imbalance between the semi-local (GGA) functional and...
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Mechanistic Insights into Reactive Zeolite-Water Interactions
Benešová, Tereza ; Heard, Christopher James (advisor) ; Maldonado Dominguez, Carlos Mauricio (referee)
Title: Mechanistic Insights into Reactive Zeolite-Water Interactions Author: Tereza Benešová Department: Department of Physical and Macromolecular Chemistry Supervisor: Christopher Heard, PhD. Abstract: An in silico investigation of zeolite-water interactions was undertaken using a combined static and dynamic approach within density functional theory. Two periodic models of zeolite chabazite were used, purely siliceous and aluminosilicate in order to explain the different behaviour of water near Si-O-Si and Al-O-Si bridges. One or two water molecules per supercell of the model were used, corresponding to experimental conditions of steaming. Under such conditions, water can interact with zeolites by non-reactive adsorption but also by reactive interactions such as hydrolysis and oxygen exchange between water and the framework. The main goal of the study was to explain oxygen exchange at an atomistic level. The viable mechanisms of oxygen exchange were established. These mechanisms are different for Si-O-Si and Al-O-Si bridges but for both of them oxygen exchange is initiated by partial hydrolysis of the framework. After this hydrolysis, oxygen exchange heals the framework while incorporating into it the oxygen that originated from the water. Both established mechanisms are competitive with non-exchange...
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Theoretical insights into encapsulated noble metals
Hou, Dianwei ; Heard, Christopher James (advisor) ; Logsdail, Andrew (referee) ; Rubeš, Miroslav (referee)
Noble metals are widely used in industry due to their excellent catalytic and optical properties. Because of limited reserves and high prices, it is desired to make effective use of every atom. It has been possible in recent years to produce subnanometer clusters or even isolated atoms, despite their low resistance against sintering. Furthermore, it has been recently established that the encapsulation of single atoms and subnanometer noble metal clusters can be achieved via trapping at metal oxides, ranging from two-dimensional layered materials to the void space within the pores of zeolites. However, neither the atomistic mechanisms of atom/cluster trapping, nor the means by which they may be optimized are known. Furthermore, the relationship between the physical and electronic state of trapped atoms/clusters and their reactive properties in catalysis are currently only weakly understood. In this thesis, we used theoretical methods ranging from global structure optimization to kinetic Monte Carlo to identify the roles of cluster size, charge state, and the present and type of common adsorbents on the stability, catalytic and optical properties of subnanometre-sized noble metal clusters trapped at metal oxides. This thesis takes the form of three sections: (1) Structure, stability, and migration...
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Theoretical investigation of water-zeolite interactions under steaming conditions
Benešová, Tereza ; Heard, Christopher James (advisor) ; Fišer, Jiří (referee)
The thesis is focused on theoretical study of hydrolysis and isotopic oxygen exchange in zeolite chabazite under steaming conditions. The theoretical study was performed by the methods of computational chemistry, namely density functional theory. Reactions of water with zeolites were investigated within the periodic model with chabazite supercell consisting of 36 Si/Al tetrahedra. Reactivity was investigated for one or two water molecules corresponding to the conditions relevant to high-temperature steaming. Relevant mechanisms of isotopic oxygen exchange were found and their competitiveness with hydrolysis was discussed.
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Theoretical investigation of water-zeolite interactions under steaming conditions
Benešová, Tereza ; Heard, Christopher James (advisor) ; Fišer, Jiří (referee)
The thesis is focused on theoretical study of hydrolysis and isotopic oxygen exchange in zeolite chabazite under steaming conditions. The theoretical study was performed by the methods of computational chemistry, namely density functional theory. Reactions of water with zeolites were investigated within the periodic model with chabazite supercell consisting of 36 Si/Al tetrahedra. Reactivity was investigated for one or two water molecules corresponding to the conditions relevant to high-temperature steaming. Relevant mechanisms of isotopic oxygen exchange were found and their competitiveness with hydrolysis was discussed.
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