WorldCat Identities

Chizallet, Céline (1980-....).

Overview
Works: 19 works in 20 publications in 2 languages and 21 library holdings
Roles: Opponent, Other, Thesis advisor, Author
Publication Timeline
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Most widely held works by Céline Chizallet
Nature et réactivité des sites basiques de l'oxyde de magnésium : rôle des hydroxyles : approche mixte expérimentale et théorique by Céline Chizallet( Book )

2 editions published in 2006 in French and held by 3 WorldCat member libraries worldwide

Développement d'outils de modélisation des surfaces d'alliages et leur application à la cinétique en catalyse hétérogène by Ruben Staub( )

1 edition published in 2020 in English and held by 1 WorldCat member library worldwide

Cette thèse se focalise sur le développement d'outils pour l'étude fondamentale des interactions latérales au travers de multiples projets : D'un point de vue quantique, les effets énergétiques des interactions chimiques sont décomposables rigoureusement en utilisant des orbitales moléculaires absolument localisées (ALMO). Au cours de cette thèse, une approximation de champ moyen a été développée et implémentée dans CP2K afin d'unifier le formalisme ALMO avec la théorie des états mixtes dans une description DFT, permettant d'étendre l'analyse en composantes énergétiques aux systèmes métalliques.D'un point de vue purement topologique, un nouvel algorithme de détermination de liaisons chimiques (ASANN) a été développé durant cette thèse. Au travers d'un simple terme correctif, ASANN étend l'algorithme de référence SANN aux systèmes présentant une anisotropie locale, sans introduire aucun paramètre. Les nombres de coordination ainsi produits sont particulièrement adaptés pour la descriptions d'interfaces. Ces points de vue complémentaires se combinent sous la forme d'un Hamiltonien effectif basé sur les interactions latérales. Un nouvel outil non-stochastique a été développé et implémenté durant cette thèse, utilisant des algorithmes d'apprentissage par renforcement pour l'entraînement automatique de tels modèles destinés à simuler un système à N corps sur surface réactive. Cet outil repose sur l'adaptation d'un UCT avec une pré-exploration guidée par le modèle en cours d'apprentissage. La mise à jour d'un tel modèle linéaire a été optimisée par la formulation d'un nouvel algorithme de résolution des moindres carrés récursifs exploitant les déficiences de rang
Mechanisms and kinetics of alkenes isomerization and cracking in chabazite zeolite quantified by constrained ab initio molecular dynamics by Jérôme Rey( )

1 edition published in 2019 in English and held by 1 WorldCat member library worldwide

A multiscale approach applied to oxidative heterogeneous catalysis on highly dispersed Pt/Al2O3 by Alexis Sangnier( )

1 edition published in 2018 in English and held by 1 WorldCat member library worldwide

This work tackles at a better understanding of oxidation catalysis on highly dispersed Pt/Al2O3 surface. This thematic is of great interest for depollution catalysis, for hydrocarbon selective oxidation or even for fuel cell developments. Adsorption and oxidation phenomena were studied with a multi-scale approach. Experimental evaluation of isolated phenomenon were performed using temperature programmed adsorption/reaction coupled with mass spectrometry, operando FTIR and microGC. Ab initio molecular modelling investigations were undertaken to handle the microscopic behaviour of adsorbate/catalyst/support interactions. Thermodynamic data were integrated into exhaustive micro-kinetic models that allow to compare experiments and modelled data. Three systems were fully explored: (i) the dissociative adsorption of O2 into atomic oxygen, (ii) adsorption of carbon monoxide and (iii) oxydation of CO towards CO2. The impact of the catalyst structuration has been discussed with ideal surfaces such as Pt(111). Light hydrocarbons oxidations such as methanol and propene were also investigated in a preliminary way. Surface reaction mechanism generator was specially developped to handle exhaustive hydrocarbon oxidation surface reactions
Ab initio Molecular Modelling of the Dealumination and Desilication Mechanisms of Relevant Zeolite Frameworks by Marius-Christian Silaghi( )

1 edition published in 2014 in English and held by 1 WorldCat member library worldwide

Zeolites are crystalline microporous aluminosilicates widely used in refining, petrochemistry and biomass conversion. However, diffusion limitation and confinement effect can promote the formation of undesired products. The introduction of mesopores by dealumination and/or desilication ("hierarchical zeolites") is a possible solution widely used experimentally. Nevertheless, the mechanisms of these demetallation reactions are poorly described at the molecular scale. We determine the mechanisms of the formation of extraframework Al species (EFAL) for zeotypes MOR, FAU, MFI and CHA occurring during the dealumination process, possibly associated with desilication. First-Principles periodic density functional theory (DFT) and hybrid QM/QM calculations have been employed in order to analyze full reaction paths leading to extraframework species and to quantify the activation energies of the determining steps. It has been demonstrated that the initiation of an Al-O(H) bond break takes place via water adsorption on the Al atom in anti-Position to the Brønsted acid site, via a penta- or tetra-Coordinated Al species. Such species are shown to be at the initiation of the Al dislodgement from the zeolitic framework. Despite a strong structural heterogeneity of T sites, we determined Brønsted-Evans-Polanyi (BEP) relationships for the entire dealumination pathway. Moreover, it is shown that not only the initiation and propagation mechanisms are primordial for the understanding of an Al extraction, but also the confinement effect on EFAL species within the zeolites cavities. Finally, from the energy profile of combined dealumination/desilication pathways, we show that it is thermodynamically favoured to extract extraframework Si species (EFSI) in the course of dealumination
Synthesis and characterisation of zeolites, their application in catalysis and subsequent rationalisation : methanol-to-olefins (MTO) process with designed ZSM-5 zeolites by Pit Losch( )

1 edition published in 2016 in English and held by 1 WorldCat member library worldwide

This work revolved around the synthesis, characterisation and application of zeolites in heterogeneous catalysis. In some cases, counterintuitive observations and results needed a thorough rationalisation, which allowed a truly continuous improvement, or rational design of a catalyst for a given reaction. Zeolites are crystalline and microporous aluminosilicates, which are defined and differ one from another through their 3D arrangement of tetrahedra (SiO4 and AlO4).It has been aimed to design heterogeneous catalysts for reactions that fit in the concepts of a sustainable chemistry. Thus, this works describes and tried to respect the concepts of green chemistry and carbon upgrading. Remarkably, during this thesis the feedback looped continuous improvement approach has led twice to adapted catalysts for a catalytic chemical transformation: the liquid-solid continuous flow halogenation of aromatics was best performed with nanosized H-*BEA zeolites exhibiting a hierarchical porosity. In contrast, the gas-solid Methanol-to-Olefins (MTO) process needed an unusual catalyst. Indeed based on our study, large and perfectly crystalline H-ZSM-5 crystals with a disperse Brønsted acidity were the optimum catalyst
Mise en forme de zéolithes : contrôle des propriétés acides des zéolithes et description de l'interface zéolithe / liant by Coralie Demaret( )

1 edition published in 2019 in French and held by 1 WorldCat member library worldwide

Zeolites are crystalline and microporous aluminosilicates with an ordered and regular structure of molecular dimension. ZSM-5 zeolites are widely used in the industry as acid catalysts but their commercial application requires millimeter-sized bodies for mechanical strength and dilution of the zeolite acidity mainly, by addition of binder, peptizer... Shaping of zeolite is the key step of the process for the industrialization of a catalyst because the additives may modify the intrinsic properties of zeolites after shaping. The aims of this PhD thesis are to identify and rationalize the physico-chemical impacts of shaping on the zeolite properties by studying the accessibility, the concentration and the strength of acid sites, as well as to describe the zeolite/binder interface. To do this, a multi-technical approach was set up. It combines model shaped materials, by varying the type of binder and ZSM-5 zeolite, textural, spectroscopic (IR, NMR) and acid characterizations, microscopy and catalytic testing. The characterization of zeolites used in this study (various crystal sizes and Si/Al ratios) was carried out prior of those of shaped materials. Large crystals have been shown more acid but less active in catalysis. Some of Al of the small crystals form aluminols whose acidity is weaker than that of bridging sites. Moreover, all the bridging sites do not contribute to the catalytic reaction, only a part of the crystal is efficient. During this work, two types of binders were used: alumina and silica which are widely used in the industry. The strategy was to highlight, in a first step, the shaping impacts on a ZSM-5 and a given binder and then, to estimate the impact of the zeolite nature (crystal size and Si/Al ratio). For the alumina-type binder, a partial pore blocking is suspected, independently of the crystal size and the Si/Al ratios. A phenomenon of alumination of the zeolite structure was found. For the silica-type binder, the critical parameter is the content of sodium cations inside the binder before the shaping. An ion exchange phenomenon was highlighted and the acid and catalytic properties of the materials collapse but in a reversible way. This impact increases when the crystal size decreases and when the Si/Al ratio increases
Réactivité catalytique à haut recouvrement : une approche théorique by Sarah Gautier( )

1 edition published in 2015 in English and held by 1 WorldCat member library worldwide

Petroleum industry has a strong interest in the selective hydrogenation of polyunsaturated hydrocarbons. This reaction is catalyzed by metallic particles or alloys and happens under pressure of hydrogen. In this work, we study the selective hydrogenation of butadiene into 1-butene, on two model catalysts which are Pt(111) and Sn/Pt-Pt(111). For this, we used the VASP code (Vienna Abinitio Simulation Package) that allows to perform periodic calculations in the framework of the Density Functional Theory (DFT). The choice of the catalysts was driven by the experimental and industrial communities who mostly use platinum because of its high activity, or alloys such as tin-platinum alloy, less active but more selective. Butadiene hydrogenation was already modeled in the past but only at T=0 K and without taking into account the real pressure conditions of the reactants. Our aim is to understand the impact of the reaction conditions which is why we ran this study at T and P conditions close to the one used experimentally, e.g. 300-400 K et 1-10 bar. For this, we setup a thermodynamic model to evaluate in a first step the surface composition when the reaction occurs. It came out that the most stable surface configuration corresponds to a coverage of 1 ML of hydrogen which suggests an Eley-Rideal type mechanism. Then we studied the kinetic aspect of this reaction and we calculated the hydrogenation pathways for different coverages of hydrogen. We concluded that there is a strong competition between the sensed mechanism, called Langmuir-Hinshelwood mechanism and implying strongly adsorbed species, and the Eley-Rideal mechanism, proposing a weak adsorption of one of the two reactants
Biomass reactions on heterogeneous catalysts : computational studies on surface determination and reactivity by Qingyi Gu( )

1 edition published in 2019 in English and held by 1 WorldCat member library worldwide

In the context of biomass valorization by heterogeneous catalysis, computational chemistry is key to provide guidance to establish the nature of the active sites in combination with experimental characterizations. Then, the reaction mechanism can be studied to determine the rate determining transition state and intermediate and further design in silico better catalysts. We implemented this approach in several reactions involving alcohols that are key in the shift from a petroleum chemical feedstock to a biomass-based feedstock. Firstly, we focused on liquid phase alcohol oxidation by oxygen, a reaction that generally requires an alkaline environment, which is detrimental to the atom economy of the process since it generates the carboxylate salt instead of the carboxylic acid. We proposed a model of metal/basic water interface that includes the adsorption of hydroxide anion. It charges the metallic surface and modifies its catalytic activity. This model was first validated comparing the predicted activity of Au and Pt in presence and in absence of a base, and then used oxidation of alcohol ethoxylates by bimetals. Then, we switched to gas phase dehydration of C3 and C4 alcohols using phosphate-based catalysts. The modeling of the surfaces was based on experimental characterizations. The molecular coverage of water on the surface in function of the pressure and temperature was established using ab initio thermodynamic. The simulations of infrared spectra of CO, NH3 and C2H2 adsorption allowed us to identify the acido-basic sites which play an important role in the reaction mechanism investigation that followed
Définition à l'échelle atomique de la surface externe de la zéolithe ZSM-5 et de son interface avec le liant by Laureline Treps( )

1 edition published in 2020 in English and held by 1 WorldCat member library worldwide

Zeolites are nanoporous aluminosilicates crystals of prominent fundamental and industrial importance. Among these, ZSM-5 is one of the most investigated solid, with paramount industrial use, that can be obtained in various forms. Some of these (hierarchical forms, nanoslabs, nanosheets and nanocrystals) exhibit a very high surface over volume ratio which make them useful for multiple industrial processes. The shaping is used to adapt ZSM-5 (and zeolites in general) to the needs of the industrial reactors. Empirically, preparing a technical zeolite is a strong industrial know-how, but with limited physic-chemical understanding of the zeolite-binder interface. Periodic Density Functional Theory (DFT, VASP, PAW, PBE dDsC) calculations of the relative stability of relevant surface orientations for silicalite and ZSM-5 crystals ((100), (010) and (101)) were performed at different hydration levels thanks to ab initio thermodynamics. Their relative acidities (pyridine and di-tertbutylpyridine adsorption) and spectral features (vibration modes, NMR chemical shifts) are determined. The interaction of the most relevant ones with binders (alumina, silica) is simulated ab initio, and an empirical reactive force field (ReaxFF) is built on purpose to model larger scales. Several kinds of surface sites have been identified. Bridging Al-OH-Si are present at the pore mouth, of similar or higher stability with respect to bulk sites. These are not stable at the outermost surface, where the following groups prevail: Si-OH, Al-OH and most importantly water adsorbed on aluminum Al-(H2O)(OH)n. Models of pyridine and 2,6-ditertbutylpyridine adsorption show that the acidity of the bridging groups is stronger than the other, and more particularly with a strong confinement. Al-(H2O)(OH)n surface site are shown to be the most stable at the external surface of ZSM-5 and are studied upon the hydration and dehydration of the ZSM-5 external surfaces. The results issue from these DFT simulations are compared to FT-IR, 1H NMR, and pyridine/2,6-ditertbutylpyridine adsorption experiments conducted at IFPEN. The interaction between zeolite and binders (silica, alumina) is first modeled by the interaction of the zeolite with small components like Si(OH)4, Na+ - present in some silica sources - and Al(OH)3(H2O). The results show that alumina components are more strongly attracted by the aluminum of the zeolitic network than silicic species. Na+ binds more strongly with the zeolite rather than silica and these results are once more compared to experimental data. The reactive force field parameters optimization is allowing to model larger external zeolite surfaces that are in contact with more realistic binder surfaces. All these results provide a rational understanding of a large set of experimental observations from the literature, that remained so far poorly understood. These findings are likely not limited to the case of the MFI framework (some of them already appeared to be valid for zeolite Beta), as our conclusions are mainly dictated by local topology aspects. The zeolite we investigate and the reactive sites we reveal are of both fundamental and industrial importance
Impact of the topology of the zeolite structure on the mechanism and selectivity of ethylcyclohexane bifunctional isomerization : experiments, ab initio calculations and multi-scale kinetic modelling by Ester Gutierrez Acebo( )

1 edition published in 2018 in English and held by 1 WorldCat member library worldwide

The paraxylene (pX), used in the manufacture of terephtalic acid for the production of nylon, is mainly produced by isomerization of the C8 aromatic cut. The latter is mainly composed of the three xylene isomers (para, ortho and meta) and ethylbenzene (EB). EB is converted into xylenes by mean of a bifunctional catalyst comprising both an acid function, such as EU-1 zeolite, and a hydro-dehydrogenating function (HD / DHD), such as platinum. The hydrogenation of EB also leads to the production of ethylcyclohexane, which can undergo undesired ring-opening and cracking reactions on the acid function of the catalyst. In this work, we tried to understand the factors influencing the selectivity of the bifunctional catalyst in the hydroconversion of ethylcyclohexane (ECH), and to identify very selective zeolitic acid phases. The effect of parameters such as the ratio and proximity between acid and HD / DHD sites, the location of acid sites within the zeolite network, and the topology of this zeolite network, was evaluated. Catalytic studies have been carried out over bifunctional catalysts series based on the EU-1 zeolite, and interpreted considering ab initio calculations focused on the isomerization and ring-opening mechanisms of ECH on the EU-1 acid phase. The integration of thermokinetic data (determined by ab initio calculations) in a mean field kinetic model made it possible to validate the approach and to identify the key reaction steps dictating the selectivity. A rational screening of zeolite structures was then proposed to identify the influential topological parameters
On the surface structures and catalytic properties of Al-based intermetallics by Corentin Chatelier( )

1 edition published in 2020 in English and held by 1 WorldCat member library worldwide

Replacing noble metal (Pd, Pt, Au) catalysts with inexpensive, environmentally harmless, active, selective, and stable substitutes is a big challenge for the chemical industry. Several aluminium-based complex intermetallic compounds have shown promises for alkynes and alkenes hydrogenation reactions, which are of interest in the chemical industry. It is the case for Al5Co2, Al13Co4 and Al13Fe4 quasicrystalline approximants. The study of their catalytic properties demands different approaches, both theoretical and experimental, in order to determine first their surface structures under ultra-high vacuum or reaction conditions, then their catalytic properties. The combination of surface science experiments (scanning tunneling microscopy, surface X-ray diffraction) and theoretical chemistry calculations (surface energies, adsorption energies and reaction pathways) allows for a better understanding of the key parameters behind the promising catalytic properties of these materials
Catalyst supports with hierarchical and radial porosity : preparation, characterization and catalytic evaluation by Alejandra Bueno( )

1 edition published in 2019 in English and held by 1 WorldCat member library worldwide

The vast majority of chemical processes are catalytic. Within the heterogeneous catalysis, industrial catalysts are bodies whose size ranges between 1 mm to 1 cm. For most catalysts, the active phase (i.e. metal nanoparticles) is dispersed in a mesoporous support having a high specific surface area. To overcome the problem of internal diffusional limitation, a secondary network of macropores is introduced within the catalyst support. This improves the diffusion of substrates. However, in the case where the catalytic reaction is particularly fast, the diffusion inside the porous support can remain limiting (Thiele modulus), resulting in a loss of catalytic effectiveness. The objective of this thesis is to study the catalytic effectiveness of a new alumina-based support shaped into spherical pellets, owing a radial macroporosity. In order to quantify the impact of this new porous structure, two model catalytic reactions were chosen to test the catalysts: CO oxidation and isooctane cracking. The catalytic activity was compared to reference commercial supports owing hierarchical porosity. For both reactions, the new support with radial porosity increases the activity from 25 to 95% approximately. On the basis of a fine characterization of the porosity of the beads (adsorption N2-77k, porosimetry Hg, X-ray microtomography), the catalytic activities were modeled. We conclude that the impact on the catalytic activity is essentially due to the radial porous design
Preparation of amorphous silica-aluminas with enhanced acidic properties and spectroscopic identification of their acid sites by Xiaojing Jin( )

1 edition published in 2017 in English and held by 1 WorldCat member library worldwide

Des silice-alumines (SA) avec des propriétés acides améliorées et une fraction plus élevée d'aluminium acides ont été préparées en utilisant deux stratégies de synthèse. Leurs propriétés texturales ont été étudiées par physisorption de N2 et leurs propriétés acides par suivi FTIR de l'adsorption de molécules sondes (pyridine ou CO). Par ailleurs, la réaction d'isomérisation du 33DMB1 a été utilisée pour caractériser leurs performances catalytiques et leurs propriétés acides. La première stratégie de synthèse a été de désaluminer des silice-alumines commerciales avec de l'acetylacetone ou de l'acide citrique (CA). CA est plus actif et plus sélectif que Acac et permet de retirer jusqu'à 87% des Al initialement présents tout en augmentant la quantité de sites acides (jusqu'à 41%) et en multipliant par 5 la fraction d'Al acides. La seconde stratégie a été de greffé des précurseurs d'aluminium (Al(OPri)xL3-x, TIBA, DiBAH) sur des silices. Toutes les SA obtenues par greffage présentent une activité catalytique plus élevées que les SA commerciales et la zéolithe, mais seules certaines de SA obtenues par greffage de DiBAH ont des sites acides de Bronsted forts. Des SA représentatives de ces deux séries ont été caractérisées par RMN, avec comme objectif d'étudier la structure des sites acides en utilisant des séquences RMN 1D et 2D, homo- et héteronucléaires impliquant 1H et 27Al. Cette étude a mis en évidence: (i) la présence, pour la plupart des SA, de deux phases, l'une d'alumine, l'autre de silice alumine (27Al DQ-SQ NMR); (ii) une localisation des atomes d'Al près de la surface sur la base de leur flexibilité de coordination 27Al NMR (DP and 3Q MAS); (iii) l'implication possible des AlV (en plus des AlIV) dans les sites acides de Bronsted (27Al-1H D-HMQC 2D NMR); (iv) la probable différence de structure des sites acides des SA par rapport à ceux des zéolithes (1H-27Al REAPDOR)
Linear energy relations for biomass transformation under heterogeneous catalysis : a fast prediction of polyalcohol dehydrogenation on transition metals by Jérémie Zaffran( )

1 edition published in 2014 in English and held by 1 WorldCat member library worldwide

Biomass valorization is an interesting alternative to fossil resources, which is frequently performed via heterogeneous catalysis. Designing new catalysts is a challenging task that can be significantly accelerated in silico. However, biomass molecules are often complex and highly oxygenated, hence rendering calculations more difficult and time consuming. Among these compounds, polyols are particularly important. We developed linear relations of the Brønsted-Evans-Polanyi (BEP) type from the DFT study of C-H or O-H bond dissociation elementary steps for a family of monoalcohol molecules on metallic catalysts (Co, Ni, Ru, Rh, Pd, Ir, Pt). Such relations aim at predicting activation energies from reaction energies. The accuracy of the obtained linear energy models is better than 0.10 eV on the sampling set. Then, the relations were applied for the prediction of the dehydrogenation elementary steps of glycerol, chosen as a prototype of polyalcohols, with an accuracy better than 0.10 eV and with a systematic error around ±0.10 eV for Rh. Keeping in mind that the main difference between glycerol and monoalcohols comes from intramolecular H-bonds present in the former, we designed linear relations for water-assisted dehydrogenation of monoalcohols. These new relations allowed us to improve the prediction on glycerol and to eliminate the systematic deviation in the case of OH bond breaking. Even if in this study we focused on glycerol dehydrogenation, similar methods may be applied to other polyols with other chemical reactions, and considerably speed up the computational design of solid catalysts. This work paves the way for the development of novel numerical techniques to address the issue of biomass conversion
Tuning the Metal-Support Interaction by Structural Recognition of Cobalt-Based Catalyst Precursors1( )

1 edition published in 2015 in English and held by 1 WorldCat member library worldwide

Etude théorique de l'effet des propriétés acido-basiques de l'alumine-gamma sur la réactivité de nano-agrégats métalliques by Christophe Mager-Maury( )

1 edition published in 2011 in French and held by 1 WorldCat member library worldwide

New acid zeolites obtained from silicogermanates by Elsy El Hayek( )

1 edition published in 2020 in English and held by 1 WorldCat member library worldwide

Zeolites are microporous crystalline aluminosilicates composed of three-dimensional arrangements of SiO4 and AlO4 tetrahedra. These materials have various applications in the fields of adsorption, catalysis, separation and ion exchange. The introduction of germanium during the synthesis of these zeolites is a strategy for accessing new structures, sometimes with extra-large pores, attractive for the catalytic transformation of bulky molecules. However, a major remaining challenge is the substitution of germanium for aluminum to generate structures with compensation cations assuring the acidic activity. Also, microporous silicogermanates are often unstable after removal of the organic structure directing agents, which limits their use. To stabilize these silicogermanates, recently, two experimental post-treatment approaches were developed. The first approach allows the initial structure of the parent zeolite to be maintained while the second leads to the creation of new stable structures exhibiting smaller pores. These post-treatments consist on reducing the Ge content by leaching the zeolite with acids, sometimes accompanied by external Si or Al source or by the direct substitution of Ge for other elements. Herein, a combination of theoretical calculations (DFT, Density Functional Theory) and experimental work (synthesis, characterization, catalysis) is used to explore the stabilization of silicogermanates. The ab initio study shows that all silicogermanates having structural codes attributed by the International Zeolite Association and their (alumino)silicates analogues are intrinsically stable. It also indicates that substitution of Ge for Si or Al is possible thermodynamically and is favorable using chloride precursors. As a consequence, a silicon tetrachloride treatment unit was used for the first time to substitute Ge for Si experimentally. This treatment led to the stabilization of the crystalline UTL structure of the IM-12 zeolite. Further treatments using polyaluminum chloride or trichloride aluminum solutions succeeded in incorporating aluminum in the zeolite framework. Various elemental and physicochemical techniques (XRD, N2 physisorption, XRF, ICP, FTIR and MAS NMR) were undertaken to characterize the materials along the treatment procedure. DFT models of the bulk and the external surfaces of the UTL structure with different elemental composition were build and helped assigning the experimental of the MAS NMR spectra. Finally, the obtained materials were tested as acid phases in the bi-functional hydroisomerization of n-decane and n-hexadecane, reflecting promising catalytic activity. This work opens perspectives for the catalytic use of stable derivatives of silicogermanate zeolites
Modelling nano-oxide materials with technological and environmental relevance : silica, titania and titanosilicates by Andi Cuko( )

1 edition published in 2018 in English and held by 1 WorldCat member library worldwide

In this thesis we focus on modelling of titania, silica and titanosilicate based nano materials because of their technological importance as they are employed in heterogeneous (photo-)catalysis, in electronics gas-sensing etc. to cite a few. For such systems, we firstly performed global optimization studies in gas-phase and water containing environments in order to identify the structures of nanoparticles. Secondly, we studied structural, energetic and electronic size-dependent properties of such nanoparticles as well as their reducibility, extrapolating up to the bulk macroscopic level in some cases. For such characterization we use accurate quantum mechanical methods based on the Density Functional Theory (DFT). Our results point to a series of important predictions such us: i) the crystallinity of titania nanoparticles, which is the key property for the photoactivity, is predicted to emerge when nanoparticles become larger than 2.0-2.5 nm; ii) the mixing of titania and silica to form titanosilicates is found be thermodynamically favorable at the nanoscale, contrary to the bulk; iii) the hydration of silica and titania nanoclusters, which plays an important role in the aggregation and nucleation process during the synthesis of larger nanoparticles, is controlled by environmental factors such as temperature and water vapor pressure as predicted from calculated phase diagrams
 
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Alternative Names
Céline Chizallet wetenschapper

Languages
English (16)

French (4)