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Wright, P. A. "The structure of zeolites and the zeolite-sorbate complex." Thesis, University of Cambridge, 1985. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.372290.
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Simancas, Coloma Jorge. "Synthesis and Characterization of Zeolitic Materials Using Phosphorous Organic Structure Directing Agents." Doctoral thesis, Universitat Politècnica de València, 2021. http://hdl.handle.net/10251/171267.
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[ES] Las zeolitas son materiales cristalinos microporosos con canales y tamaños de poro de dimensiones moleculares. La estructura y composición de las zeolitas les confiere interesantes propiedades que permiten su aplicación en una amplia gama de aplicaciones industriales como adsorción, separación o catálisis. La síntesis de zeolitas es la etapa más importante para el control de la estructura y composición de las zeolitas y, por tanto, crítica para la optimización de sus propiedades.
Esta tesis se ha centrado en la síntesis de zeolitas utilizando compuestos que contienen fósforo (cationes fosfonio y aminofosfonio) como Agentes Directores de Estructura (P-ADE). El uso de compuestos fosforados influye en la cristalización y propiedades de las zeolitas obtenidas en comparación con las zeolitas obtenidas con cationes de amonio clásicos.
Los compuestos fosforados se eligieron debido a su diferente química y estabilidad con respecto a los cationes de amonio clásicos comúnmente usados en la síntesis de zeolitas. Estos aspectos se estudiaron con un estudio comparativo de diferentes cationes de amonio y fosforados.
Los compuestos de fósforo utilizados en este trabajo han dado lugar a nuevas estructuras cristalinas (ITQ-58 e ITQ-66) y han abierto nuevas vías de síntesis de zeolitas ya conocidas (RTH, IWV y DON), ampliando su gama de composiciones químicas.
La descomposición térmica de los P-ADE confinados dentro de las zeolitas da lugar a la formación de especies de fósforo extra-red que permanecen dentro de los canales y cavidades de las zeolitas. Estas especies modulan las propiedades ácidas y de adsorción de los materiales finales dependiendo de los tratamientos post-síntesis. En este trabajo se ha estudiado una ruta para la incorporación de cantidades controladas de fósforo durante la etapa de síntesis. Esto ha permitido controlar la adsorción y las propiedades ácidas en las zeolitas de poro pequeño, lo que no se puede lograr mediante metodologías de post-síntesis.<br>[CA] Les zeolites són materials cristal·lins microporosos amb canals i mides de porus de dimensions moleculars. L'estructura i composició de les zeolites els confereix interessants propietats que permeten la seua aplicació en una àmplia gamma d'aplicacions industrials com adsorció, separació o catàlisi. La síntesi de zeolites és l'etapa més important per al control de l'estructura i composició de les zeolites i, per tant, crítica per a l'optimització de les seues propietats.
Aquesta tesi s'ha centrat en la síntesi de zeolites utilitzant compostos que contenen fòsfor (cations fosfoni i aminofosfoni) com a agents directors d'estructura (P-ADE). L'ús de compostos fosforats influeix en la cristal·lització i propietats de les zeolites obtingudes en comparació amb les zeolites obtingudes amb cations d'amoni clàssics.
Els compostos fosforats es van triar a causa de la seua diferent química i estabilitat pel que fa als cations d'amoni clàssics utilitzats en la síntesi de zeolites. Aquests aspectes s¿estudiaren amb un estudi comparatiu de diferents cations d'amoni i fosforats.
Els compostos de fòsfor utilitzats en aquest treball han donat lloc a noves estructures cristal·lines (ITQ-58 i ITQ-66) i han obert noves vies de síntesi de zeolites ja conegudes (RTH, IWV i DO), ampliant la seua gamma de composicions químiques.
La descomposició tèrmica dels P-ADE atrapats dins de les zeolites dona lloc a la for-mació d'espècies de fòsfor extra-xarxa que romanen dins dels canals i cavitats de les zeolites. Aquestes espècies modulen les propietats àcides i d'adsorció dels materials finals depenent dels tractaments post-síntesi. En aquest treball s'ha estudiat una ruta per la incorporació de quantitats controlades de fòsfor durant l'etapa de síntesi. Això ha permés controlar l'adsorció i les propietats àcides en les zeolites de porus petit, el que no es pot aconseguir mitjançant metodologies de post-síntesi.<br>[EN] Zeolites are microporous crystalline materials with channels and pore openings of molecular dimensions. The structure and composition of zeolites confers them interesting properties that allow their application in a wide range of industrial applications as adsorption, separation or catalysis. The synthesis of zeolites is the most important stage to control the structure and composition of zeolites, and thus, critical to optimize their properties.
This thesis has been focused on the synthesis of zeolites using phosphorous containing compounds (phosphonium and aminophosphonium cations) as Organic Structure Directing Agents (P-OSDA). The use of these phosphorous compounds influence the crystallization and properties of the obtained zeolites compared to zeolites obtained with classical ammo-nium cations.
Phosphorous compounds were chosen because of their different chemistry and stabil-ity properties respect to classical ammonium cations commonly used in the synthesis of zeo-lites. These aspects were studied in a comparative study with different ammonium and phosphorous cations.
The phosphorous compounds used in this work have yielded new crystalline structures (ITQ-58 and ITQ-66) and opened new routes for the synthesis of already known zeolites (RTH, IWV and DON), widening their chemical composition range.
The thermal decomposition of the P-OSDAs entrapped inside the zeolites yields to the formation of extra-framework phosphorus species that remain inside the channels and voids of the zeolites. These species modulate the adsorption and acid properties of the final materials depending on the post-synthesis treatments. In this work, a route for the incorporation of controlled amounts of phosphorus during the synthesis stage has been studied. This has allowed to control the adsorption and acid properties in small pores zeolites, which cannot be achieved by post-synthesis methodologies.<br>I wish to firstly acknowledge the Spanish Government for the necessary funding for
the FPI pre-doctoral fellowship (BES-2013-062999). Also, this thesis would not have been
possible without the infrastructures provided by the UPV and the CSIC staff, fused into the
ITQ. Furthermore, I want to acknowledge the Microscopy Service of the UPV for their support in sample microscopy characterization<br>Simancas Coloma, J. (2021). Synthesis and Characterization of Zeolitic Materials Using Phosphorous Organic Structure Directing Agents [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/171267<br>TESIS
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Kibby, Sarah A. M. "Applications of zeolites to organic synthesis." Thesis, University of Edinburgh, 1990. http://hdl.handle.net/1842/10989.
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The application of zoelites as catalysts for a number of organic, liquid-phase, acid-promoted reactions is discussed with reference to zeolite acidity and structure on product yield and selectivity. The zeolites described are predominantly high silica materials including Nu-2, ZSM-5, Nu-10 and EU-1 structures. Examination of the Claisen rearrangement of allyl phenyl ether has shown that it is promoted by zeolites relative to the thermal reaction and that the extent of conversion increases with zeolite acidity. In addition to the expected products, 2-allylphenol and the cyclic 2-methyldihydrobenzofuran, small quantities of the <i>para</i>-product, 4-allylphenol are detected over H-Nu-2 and (Cu(II),H)-Y zeolites. 4-Allylphenol is not detected in the thermal rearrangement and its formation in the present work is attributed to an intermolecular mechanism <i>via</i> ether cleavage. Also examined is the Fries rearrangement of phenyl acetate and phenyl benzoate. The product selectivity is compared with that over Nafion-H, an acidic, non-porous, perfluorinated ion-exchange resin. Both rearrangements are more <i>para</i>-selective when performed in the presence of zeolites. In the rearrangement of phenyl acetate a number of by-products in addition to the expected 2- and 4-hydroxyacetophenones are observed. The aldol self-condensation of acetophenone to yield β-methylchalcone and of acetophenone and benzaldehyde to yield chalcone is promoted by H-Nu-2 zeolite. The ring closure of 2-benzoylbenzoic acid to anthraquinone takes place quantitatively over H-Nu-2. The cyclisation is monitored by i.r. to completion and the product isolated by extraction or sublimation. Of those zeolites examined, H-Nu-2 is likely to be most widely applicable as a catalyst in organic synthesis because of its relatively large pore dimensions, high silica content (thermal stability) and high acidity.
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Laidlaw, Paul. "Catalysis of organic reactions by cation-exchanged zeolites." Thesis, University of Liverpool, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.366734.
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Langham, Christopher. "Heterogeneous enantioselective azirdination of alkenes using zeolites." Thesis, University of Liverpool, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.266046.
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Martin, K. "The catalysis of organic reactions by clays and zeolites." Thesis, Aberystwyth University, 1987. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.381778.
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Nearchou, Antony. "Zeolites fit for a crown." Thesis, University of Bath, 2019. https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.767594.
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Annamalai, Perushini. "Electrospinning of porous composite materials for hydrogen storage application." University of the Western Cape, 2016. http://hdl.handle.net/11394/5654.
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>Magister Scientiae - MSc<br>Due to the rapid depletion of fossil fuel reserves and the production of environmentally harmful by-products such as carbon dioxide, there is an urgent need for alternate sustainable clean energy. One of the leading candidates in this endeavour is hydrogen, which can be used as an energy carrier since it has a high energy density, zero emissions and is produced from non-depletable resources such as water. The major challenge hindering a hydrogen economy is the lack of safe and effective storage technologies for mobile applications. A prospective solution to this problem lies in the use of porous powdered materials, which adsorb the hydrogen gas. However, the integration of these powdered materials into a storage tank system, results in the pipelines being contaminated during filling cycles. This necessitates the shaping of the porous powdered materials. Among the many shaping techniques available, the electrospinning technique has been proposed as a promising technology since it is a versatile process that is easily scaled-up making it attractive for the applications of the study. Furthermore, the electrospinning process enables the synthesis of nano-sized fibres with attractive hydrogen sorption characteristics. In this regard, the current study employs the electrospinning technique to synthesise electrospun composite fibres for mobile hydrogen storage applications. After electrospinning three polymers, polyacrylonitrile (PAN) was selected as the most suitable polymer because it yielded bead-free electrospun fibres. However, the diameter of the PAN fibres was large/thick which prompted further optimisation of the electrospinning parameters. The optimised electrospinning conditions that yield unbeaded fibres within the desired diameter range (of 300-500 nm) were a PAN concentration of 10 wt%, a flow rate of 0.4 mL/h, a distance of 10 cm between the needle tip and collector plate, and an applied voltage of 8 kV. The study then progressed to the synthesis and characterisation of the pristine porous powdered materials which adsorb hydrogen gas. The porous powdered materials investigated were commercial zeolite 13X, its synthesised templated carbon
derivative (ZTC) and Zr (UiO-66) and Cr (MIL-101) based metal-organic frameworks (MOFs). ZTC was synthesised via liquid impregnation coupled with chemical vapour deposition (CVD), and the MOFs were synthesised by the modulated solvothermal method. Analysis of the ZTCs morphology and phase crystallinity show that the carbon templated process using zeolites was successful, however, ZTC was amorphous compared to crystalline zeolite template. The BET surface area was assessed with the aid of nitrogen sorption isotherms for both zeolite 13X and ZTC, and values of 730 and 2717 m²/g, respectively were obtained. The hydrogen adsorption capacity for zeolite 13X was 1.6 wt% and increased to 2.4 wt% in the ZTC material at 77 K and 1 bar. The successful synthesis of well defined, crystalline MOFs was evident from X-ray diffraction and morphological analysis. The BET surface area and hydrogen adsorption for Zr MOF were 1186 m²/g and 1.5 wt%, respectively at 77 K and 1 bar. Cr MOF had a BET surface area of 2618 m²/g and hydrogen adsorption capacity of 1.9 wt% at 77 K and 1 bar. The main focus of the study was to synthesise electrospun composite fibres that can adsorb hydrogen gas and thus provide significant insight in this field of research. As such it examined composite fibres that incorporates porous powdered materials such as zeolite 13X, ZTCs, UiO-66 (Zr) MOF and MIL-101 (Cr) MOF and investigated their ability to adsorb hydrogen gas, which have not been reported previously. The synthesis of composite fibres was achieved by incorporating the porous powdered materials into the PAN resulting in a polymeric blend that was then electrospun. Morphological analysis illustrated that the porous powdered materials were successfully supported by or incorporated within the PAN fibres, forming composite fibres. The BET surface area of the 40 wt% zeolite-PAN and 12.5 wt% ZTC-PAN composite fibres were 440 and 1787 m²/g respectively. Zr MOF and Cr MOF composite fibres had a BET surface area of 815 and 1134 m²/g, respectively. The BET surface area had reduced by 40, 34, 31 and 57% for zeolite 13X, ZTC, Zr MOF and Cr MOF, respectively after these porous powdered materials were incorporated into PAN. The hydrogen adoption capacity for 40 wt% zeolite-PAN, 12.5 wt% ZTC-PAN, 20 wt% Zr MOFPAN and 20 wt% Cr MOF-PAN composite fibres was 0.8, 1.8, 0.9 and 1.1 wt%, respectively. This decrease was attributed to the limited amount of porous powdered materials that could be incorporated into the fibres since only 40 wt% of zeolite 13X, 12.5 wt% of ZTC and 20 wt% of the MOFs were loaded into their respective composite fibres. This was due to the fact that incorporation of greater amounts of porous powdered materials resulted in a viscous polymeric blend that was unable to be electrospun. It is evident from the study that electrospinning is a versatile process that is able to produce composite fibres with promising properties that can potentially advance the research in this field thus providing a practical solution to the problem of integrating loose powdered materials into an on-board hydrogen storage system.<br>CSIR Young Researchers Establishment Fund (YREF)
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Qiu, Liyan. "Thermal properties of framework materials, selected zeolites, clathrates and an organic diol." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 2000. http://www.collectionscanada.ca/obj/s4/f2/dsk1/tape3/PQDD_0035/NQ66643.pdf.
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Kassaee, Mohamad Hadi. "Internal surface modification of zeolite MFI particles and membranes for gas separation." Diss., Georgia Institute of Technology, 2012. http://hdl.handle.net/1853/44906.
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Zeolites are a well-known class of crystalline oxide materials with tunable compositions and nanoporous structures, and have been used extensively in catalysis, adsorption, and ion exchange. The zeolite MFI is one of the well-studied zeolites because it has a pore size and structure suitable for separation or chemical conversion of many industrially important molecules. Modification of zeolite structures with organic groups offers a potential new way to change their properties of zeolites, beyond the manipulation of the zeolite framework structure and composition.
The main goals of this thesis research are to study the organic-modification of the MFI pore structure, and to assess the effects of such modification on the adsorption and transport properties of zeolite MFI sorbents and membranes. In this work, the internal pore structure of MFI zeolite particles and membranes has been modified by direct covalent condensation or chemical complexation of different organic molecules with the silanol defect sites existing in the MFI structure. The organic molecules used for pore modification are 1-butanol, 1-hexanol, 3-amino-1-propanol, 1-propaneamine, 1,3-diaminopropane, 2-[(2-aminoethyl)amino]ethanol, and benzenemethanol. TGA/DSC and 13C/29Si NMR characterizations indicated that the functional groups were chemically bound to the zeolite framework, and that the loading was commensurate with the concentration of internal silanol defects. Gas adsorption isotherms of CO2, CH4, and N2 on the modified zeolite materials show a range of properties different from that of the bare MFI zeolite. The MFI/3-amino-1-propanol, MFI/2-[(2-aminoethyl)amino]ethanol, and MFI/benzenemethanol materials showed the largest differences from bare MFI. These properties were qualitatively explained by the known affinity of amino- and hydroxyl groups for CO2, and of the phenyl group for CH4. The combined influence of adsorption and diffusion changes due to modification can be studied by measuring permeation of different gases on modified MFI membranes.
To study these effects, I synthesized MFI membranes with [h0h] out-of-plane orientation on α-alumina supports. The membranes were modified by the same procedures as used for MFI particles and with 1-butanol, 3-amino-1-propanol, 2-[(2-aminoethyl)amino]ethanol, and benzenemethanol. The existence of functional groups in the pores of the zeolite was confirmed by PA-FTIR measurements. Permeation measurements of H2, N2, CO2, CH4, and SF6, were performed at room temperature before and after modification. Permeation of n-butane, and i-butane were measured before and after modification with 1-butanol. For all of the studied gases, gas permeances decreased by 1-2 orders of magnitude compared to bare MFI membranes for modified membranes. This is a strong indication that the organic species in the MFI framework are interacting with or blocking the gas molecule transport through the MFI pores.
A detailed fundamental study of the CO2 adsorption mechanism in modified zeolites is necessary to gain a better understating of the adsorption and permeation behavior of such materials. Towards this end, an in situ FTIR study was performe.For the organic molecules with only one functional group (1-butanol, benzenemethanol, and 1-propaneamine), physical adsorption was found - as intuitively expected - to be the only observed mode of attachment of CO2 to the modified zeolite material. Even in the case of MFI modified with 1,3-diaminopropane, only physical adsorption is seen. This is explained by the isolated nature of the amine groups in the material, due to which only a single amine group can interact with a CO2 molecule. On the other hand, chemisorbed CO2 species are clearly observed on bare MFI, and on MFI modified with 3-amino-1-propanol or 2-[(2-aminoethyl)amino]ethanol. Specifically, these are carbonate-like species that arise from the chemisorption of CO2 to the silanol group in bare MFI and the alcohol groups of the modifying molecule. The possibility of significant contributions from external surface silanol groups in adsorbing CO2 chemisorbed species was ruled out by a comparative examination of the FTIR spectra of 10 μm and 900 nm MFI particles modified with 2-[(2-aminoethyl)amino]ethanol.
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Stückenschneider, Kai [Verfasser]. "Molecular Modeling of Adsorptive Interactions between Small Organic Molecules and Zeolites / Kai Stückenschneider." München : Verlag Dr. Hut, 2014. http://d-nb.info/1055863079/34.
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Morris, Samuel Alexander. "X-ray studies of zeolites and MOFs." Thesis, University of St Andrews, 2016. http://hdl.handle.net/10023/9891.
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This thesis is largely a study of the ADOR process (assembly-disassembly-organisation-reassembly) when applied to zeolite UTL. The final chapter of this thesis deals with the adsorption of the medical gases NO and CO onto the metal organic framework NiNaSIP. Chapter 4 is devoted to the disassembly and organisation steps of the ADOR process. Calcined UTL was hydrolysed using 0.1 – 12 M HCl solutions from 75 – 95 °C run over 10 mins to 72 hrs. A three step mechanism is proposed, which is comprised of an initial rapid hydrolysis that removes the majority of the interlayer constituents of UTL, causing the silica-rich layers to largely collapse. This is followed by a slow, temperature and molarity dependent, deintercalation process that sees the remainder of the interlayer material removed resulting in the full collapse of the layers to form IPC-1P. The third step is a temperature and molarity dependent rebuilding process, whereby the interlayer region is slowly rebuilt, eventually forming a precursor which upon calcination becomes IPC-2 (OKO). Chapter 5 uses the pair distribution function (PDF) technique to structurally confirm the intermediate of the ADORable zeolite UTL. The intermediate, IPC-1P, is a disordered layered compound formed by the hydrolysis of UTL in 0.1 M HCl. Its structure is unsolvable by traditional X-ray diffraction techniques. The PDF technique was first benchmarked against high-quality synchrotron Rietveld refinements of IPC-2 (OKO) and IPC-4 (PCR) – two end products of IPC-1P condensation that share very similar structural features. An IPC-1P starting model derived from density functional theory was used for the PDF refinement, which yielded a final fit of Rw = 18% and a geometrically reasonable structure. This confirms that the layers do stay intact throughout the ADOR process, and shows that PDF is a viable technique for layered zeolite structure determination. Chapter 6 examines the reassembly stage by following the in-situ calcination of a variety of hydrolysed intermediates into their three-dimensional counterparts. Beamline I11 at Diamond Light Source provided high-quality PXRD patterns as a function of temperature, which were refined against using sequential Pawley refinements to track the unit cell changes. 0.1, 1.75, 2.5 and 12 M hydrolysed lamellar precursor phases were calcined. The largest unit cell changes were observed for 0.1 M, and the smallest for 12 M. This shows that increasing the molarity must prebuild most of the interlayer connections, such that upon calcination, only minimal condensation occurs to fully connect the layers. Chapter 7 probes the uptake of the medical gases CO and NO into the metal organic framework NiNaSIP. An in-situ single-crystal XRD study was undertaken using an environmental gas cell at beamline 11.3.1 at the Advanced Light Source. NiNaSIP was first dehydrated to reveal an open nickel site, which acted as the main site of adsorption for the inputted gases. NO was observed in a bent geometry at an occupancy of 40 % and a Ni – N bond length of 2.166(16) Å. The oxygen was modelled to be disordered over two sites. CO was not fully observed, as only the carbon was able to be modelled with an occupancy of 31.2 % and a Ni – C bond length of 2.27(3) Å.
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Xu, Yiming. "Photocatalysis of supported titania on micro/mesoporous zeolites for the oxidation of organic compounds in water." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1997. http://www.collectionscanada.ca/obj/s4/f2/dsk3/ftp04/nq20777.pdf.
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Bignami, Giulia Paola Maria. "Exploiting isotopic enrichment for a solid-state NMR investigation of 'ADORable' zeolites and breathing metal-organic frameworks." Thesis, University of St Andrews, 2018. http://hdl.handle.net/10023/14202.
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This thesis combines synthetic studies for isotopic enrichment with solid-state characterisation techniques to investigate two classes of microporous materials: zeolites and metal-organic frameworks (MOFs). These materials have a wide range of successful applications, from industrial catalysis to medicine, resulting in the increasing need for both a complete understanding of their unique structural features and synthetic methods to target new frameworks. Nuclear magnetic resonance (NMR) spectroscopy, thanks to its sensitivity to the local, atomic-scale, environment and its element specificity, is applied, in combination with powder X-ray diffraction (PXRD), electron microscopy, N2 adsorption and mass spectrometry, to the study of these materials. Oxygen atoms play a crucial role in the structure and chemistry of zeolites and MOFs, making 17O NMR an excellent tool for chemical and structural investigations. However, the low natural abundance of this isotope (0.037%) and the cost of 17O-enriched reactants require the development of atom-efficient synthetic processes for isotopic enrichment. In the first part of this work, the unconventional assembly-disassembly-organisation-reassembly (ADOR) method is applied to the Ge-doped UTL framework and optimised in reduced-volume conditions for economic enrichment to obtain 17O- and 29Si-enriched UTL-derived zeolites. In situ and ex situ solid-state characterisation studies show that isotopic enrichment not only enables a more detailed spectroscopic investigation, but also provides new insights into the mechanism of the ADOR process and its sensitivity to experimental conditions. In the second part of this work, dry gel conversion synthesis and a novel steaming procedure are studied as cost-effective 17O-enrichment pathways for Al, Ga and Sc mixed-metal terephthalate MOFs. 17O solid-state NMR spectroscopy, in combination with PXRD and electron microscopy, is employed to investigate cation disorder and 17O NMR spectra are shown to be sensitive to substitution of metal centers and conformational changes upon interaction with guest molecules.
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Hong, Suk Bong. "Aromatization of n-hexane by platinum containing molecular sieves and distribution and motion of organic guest molecules in zeolites." Diss., Virginia Tech, 1992. http://hdl.handle.net/10919/39837.
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A vapor phase impregnation technique with Pt(acac)2 has been developed and used to load Pt into aluminosilicate (KL, BaKL, KBaKL, NaY, CsNaY, FAU, EMT, ZSM-12 and SSZ-24) and aluminophosphate (AIP04-5 and VPI-5) molecular sieves. 13C MAS NMR, TEM and H2 chemisorption measurements reveal that Pt can be loaded into the micropores of molecular sieves with both charged and neutral frameworks. Pt containing molecular sieves were tested as catalysts for the aromatization of n-hexane at 460 - 510°C and atmospheric total pressure in order to study the influence of Pt cluster size and support acidity/basicity, microstructure and chemical composition on activity and selectivity. High selectivity to benzene over most of the zeolite samples demonstrates that support acidity/basicity and microstructure do not contribute directly to the aromatization selectivity over Pt catalysts. A clear trend of increasing benzene selectivity with decreasing Pt cluster size is found. These observations suggest that the exceptional reactivity of Pt/KL for the aromatization of n-hexane results from the lack of any acidity in the support and the ability of zeolite L to stabilize the formation of extremely small Pt clusters. Pt/AIP04-5 and PWPI-5 show high selectivity to n-hexane with little formation of benzene while opposite is observed for Pt/SSZ-24. The differences in catalytic behavior are attributed to variations in the environment of Pt clusters which are situated in either an aluminophosphate or silicate micropore.<br>Ph. D.
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Friebe, Sebastian [Verfasser]. "Membranes based on metal-organic frameworks (MOFs) or zeolites and new membrane concepts for hydrogen purification / Sebastian Friebe." Hannover : Technische Informationsbibliothek (TIB), 2017. http://d-nb.info/1137060638/34.
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Pereira, Elen Maria Feliciano. "Híbridos ureasil-poliéter conjugados com zeólitas MFI para acetilação do glicerol /." Araraquara, 2019. http://hdl.handle.net/11449/183485.
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Orientador: Celso Valentim Santilli<br>Banca: Leila Aparecida Chiavacci Favorin<br>Banca: Eduardo Ferreira Molina<br>Resumo: Neste trabalho a metodologia sol-gel foi utilizada para a preparação de materiais híbridos orgânico-inorgânicos (HOI) à base de óxido de poli-etileno (PEO), ligado de forma covalente com o agente acoplador 3(isocianatopropil) - trietoxisilano (IsoTREOS) conjugados com um material zeolítico do tipo MFI, visando aplicações como catalisador para a reação de acetilação do glicerol e assim agregar valor a esse coproduto gerado na produção do biodiesel. O objetivo desta dissertação é demonstrar que o sinergismo entre híbridos do tipo siloxano-poliéter e as zeólitas pode ser explorado na produção de hidrogéis com atividade catalítica. As análises por Microscopia Eletrônica de Varredura (MEV) evidenciaram a homogeneidade na dispersão do material zeolítico na matriz híbrida Os difratogramas de raios-X apresentaram os picos característicos da estrutura cristalina da zeolita ZSM-5 após a conjugação com a matriz U-PEO. Os resultados de Calorimetria Diferencial de Varredura (DSC) revelaram que não ocorre uma mudança significativa na temperatura de transição vítrea (Tg), após a conjugação da matriz híbrida com a zeólita e revelaram uma diminuição do pico endotérmico associado à fusão dos domínios cristalinos do PEO1900, indicando uma possível interação matriz-zeólita. As análises por Espectroscopia no Infravermelho com Transformada de Fourier (FTIR) confirmaram a interação entre a matriz híbrida e a zeólita pelo deslocamento das bandas associadas ao oxigênio tipo éter não coordenado. Medid... (Resumo completo, clicar acesso eletrônico abaixo)<br>Abstract: In this work the sol-gel methodology was used for the preparation of organic-inorganic hybrid (HOI) materials based on polyethylene oxide (PEO) - covalently bonded with the coupling agent 3 (isocyanatopropyl) triethoxysilane (IsoTREOS) conjugate with a zeolitic material of the MFI type, aiming at applications as catalyst for glycerol acetylation reaction and thus add value to this byproduct generated in biodiesel production. The objective of this dissertation is to demonstrate that the synergism between siloxane-polyether hybrids and zeolites can be explored in the production of catalytic activity hydrogels. Scanning Electron Microscopy (SEM) analyzes showed homogeneity in the dispersion of zeolite material in the hybrid matrix. XDR patterns showed the characteristic peaks of the ZSM-5 zeolite crystal structure after conjugation with the U-PEO matrix. Differential Scanning Calorimetry (DSC) results revealed that no significant change in glass transition temperature (Tg) occurs after conjugation of hybrid matrix with zeolite and revealed a decrease in endothermic peak associated with fusion of crystalline domains of PEO1900., indicating a possible matrix-zeolite interaction. Fourier Transform Infrared Spectroscopy (FTIR) analyzes confirmed the interaction between the hybrid matrix and zeolite by shifting the bands associated with uncoordinated ether oxygen. Small-angle X-ray Scattering (SAXS) measurements showed that the starting reagents in the solketal production reaction w... (Complete abstract click electronic access below)<br>Mestre
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Borghese, Sophie. "Toward green processes organic synthesis by catalysis with metal-doped solids." Phd thesis, Université de Strasbourg, 2013. http://tel.archives-ouvertes.fr/tel-01017796.
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Nowadays, the modern chemical industry has to deal with increasing environmental concerns, including the disposal of waste and its economic impact, or the diminution of important worldwide resources such as transition metals. In this Ph.D. thesis, we aimed to bring improvement in this area by the development of green processes, based on the use of recyclable heterogeneous catalysts. By combining the catalytic properties of several metal cations with the properties of solid catalysts such as polyoxometalates or zeolites, we were able to set up new tools for organic synthesis. Silver-doped polyoxometalates proved to be very efficient catalysts in the rearrangement of alkynyloxiranes to furans. Acetals and spiroketals were synthetized by dihydroalkoxylation of alkynediols under catalysis with silver-zeolites. As a perspective, we highlighted the potential applications of such green procedures in the total synthesis of more complex molecules. The first results suggested that these environmental friendly processes should gain increasing interest in the future.
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Gebbie, James Thomas. "A theoretical study of crystal growth in nanoporous materials using the Monte Carlo method." Thesis, University of Manchester, 2014. https://www.research.manchester.ac.uk/portal/en/theses/a-theoretical-study-of-crystal-growth-in-nanoporous-materials-using-the-monte-carlo-method(d601decf-d422-42a5-b13a-dbc1e5dabf99).html.
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This work is aimed at understanding the underlying processes of crystal growth in nanoporous materials at the molecular level utilising computational modelling. The coarse grain Monte Carlo program constructed over a number of works at the CNM has shown success in modelling cubic zeolite systems. The goal of this work is to adapt the program to deal with the complexities of a wide range of different crystal systems. There have been many studies of crystal growth and many problems solved. In zeolites, however, there are still a lot of questions to answer. Growth rates and activation energies for crystal growth processes in zeolites are some of the things that remain unsolved for zeolites. Coarse grain Monte Carlo modelling simplifies the problem and can provide an insight into the underlying processes that govern crystal growth. This study focused its energetics around the formation of stable closed cage surface structures deduced from careful study of the dissolution of zeolite L terraces. Two approaches from an energetic point of view were investigated during the course of this study. The first considered the energetics from an energy of attachment point of view whilst the second focused on the energy of destabilisation with respect to crystal bulk. In this study the crystal growth of the following systems were probed computationally: LTA, SOD, LTL, ERI, OFF. Both zeolite and MOF crystal systems were studied over the course of this work. The algorithm developed in study shows some potential in being able to give insight to experimental crystal growth chemists as to how changing the rates of growth of certain cage structures would affect the overall morphology of the crystal grown. They can then utilise their knowledge of how using certain cations or templates, for example, can alter the stabilisation of certain cage structures to in effect design crystals of desired properties.
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Chin, Khin Kein. "Photophysical studies of fullerene derivatives and organic molecular nanocrystals ; and Singlet oxygen in microheterogeneous media: direct characterization in zeolites, proteins, and immunoglobulins." Diss., Restricted to subscribing institutions, 2008. http://proquest.umi.com/pqdweb?did=1779690191&sid=7&Fmt=2&clientId=1564&RQT=309&VName=PQD.
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Belarbi, Hichem. "Élaboration des zéolithes nano-structurées M-ZSM-5 (M=Cu, Cr et Fe) : Etude comparée des solides poreux minéraux et organométalliques MOFs dans l’oxydation de méthylènes benzyliques." Thesis, Montpellier 2, 2014. http://www.theses.fr/2014MON20192.
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L'énergie, le développement durable et la santé sont au cœur des préoccupations actuelles de la planète. La disparition inéluctable des énergies fossiles, les conséquences graves des émissions de gaz carbonique sur l'environnement et la santé appellent des solutions rapides et efficaces pour suppléer aux premières et minimiser les autres.Parmi les solutions envisagées la catalyse hétérogènes représentés par les matériaux poreux, ces derniers ont prouvé leur efficacité, néanmoins des obstacles sont à corriger ou à contourner tel que le problème d'inaccessibilité des molécules encombrantes dans sites des micropores de ce matériau. Dans cette thèse nous avons essayé de trouver la solution à ce problème en travaillant sur des nanostructures ZSM-5.Dans une première étape, nous avons optimisé ce matériau en l'occurrence ZSM-5, avec une réduction de la taille des particules, d'une échelle microscopique vers une autre nanométrique, ce qui nous a permis d'augmenter la surface externe après une modification de certains paramètres. Dans la deuxième étape, et afin de donner une entité catalytique à notre support (la zéolithe), nous avons activé ce matériau par l'incorporation des cations, choisis en fonction d'une réaction bien spécifique, qui est celle d'oxydation des méthylènes benzéniques. Pour ce fait nous avons élaboré différents catalyseurs pour nos réactions.Nous avons conclu cette thèse par la catalyse avec la M-ZSM-5 (M = Cu, Cr et Fe) et une étude comparative est faite avec les MOFs qui portent les mêmes cations actifs dans leur partie minérale<br>Energy, sustainable development, and health are at the heart of contemporary concerns of the planet. The inevitable disappearance of fossil fuels, the severe consequences of carbon emissions on the environment and health require quick and effective solutions to supplement the first and minimize others. Among the solutions proposed, there are porous materials which have proven their effectiveness; however, there are still obstacles to be corrected or circumvented. In this thesis, we focus on the problem of bulky molecules' inaccessibility in micro pores of the materials we wish to study. In the first part, we optimize the material in this case, ZSM-5, with a reduction in particle size to a microscopic scale to another nano, which allows us to increase the external surface after changing certain parameters. In the second step, in order to give a catalytic entity to our support (zeolite), we activate with this material incorporating cations selected according to a specific property of the benzyl methylenes oxidation reaction. For this reason we developed different method of preparation. We conclude this thesis by catalysis with M-ZSM-5 (M = Cu, Cr and Fe) and a comparative study on the method of preparation and the MOFs that bears the same cations as mineral part which constitutes the materials
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Borghèse, Sophie. "Toward green processes organic synthesis by catalysis with metal-doped solids." Thesis, Strasbourg, 2013. http://www.theses.fr/2013STRAF008/document.
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De nos jours, l’industrie chimique est de plus en plus confrontée à la question de son impact environnemental. Dans le même temps, elle doit faire face à la diminution des ressources de matières premières importantes tels que les métaux de transition, tout en respectant des contraintes économiques. Ces travaux de thèse avaient pour but de tenter de répondre à ces exigences, par le développement de méthodologies de synthèse basées sur l’utilisation de catalyseurs hétérogènes recyclables. En combinant les propriétés catalytiques de certains ions métalliques avec les propriétés de catalyseurs solides tels que les polyoxométallates ou les zéolithes, nous avons pu mettre au point de nouveaux outils pour la synthèse organique. Les polyoxométallates dopés à l’argent ont démontré leur efficacité dans le réarrangement d’alcynyloxiranes en furanes. La synthèse de spiroacétals et d’acétals par dihydroalkoxylation d’alcyne diols a été effectuée pour la première fois en catalyse à l’argent, via l’utilisation de zéolithes. En perspective, nous avons mis en évidence les applications potentielles de ces procédés verts dans la synthèse totale de molécules plus complexes. Les premiers résultats suggèrent que de telles synthèses plus respectueuses de l’environnement ont tout intérêt à être davantage utilisées à l’avenir<br>Nowadays, the modern chemical industry has to deal with increasing environmental concerns, including the disposal of waste and its economic impact, or the diminution of important worldwide resources such as transition metals. In this Ph.D. thesis, we aimed to bring improvement in this area by the development of green processes, based on the use of recyclable heterogeneous catalysts. By combining the catalytic properties of several metal cations with the properties of solid catalysts such as polyoxometalates or zeolites, we were able to set up new tools for organic synthesis. Silver-doped polyoxometalates proved to be very efficient catalysts in the rearrangement of alkynyloxiranes to furans. Acetals and spiroketals were synthetized by dihydroalkoxylation of alkynediols under catalysis with silver-zeolites. As a perspective, we highlighted the potential applications of such green procedures in the total synthesis of more complex molecules. The first results suggested that these environmental friendly processes should gain increasing interest in the future
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Haldoupis, Emmanuel. "Mulitscale modeling and screening of nanoporous materials and membranes for separations." Diss., Georgia Institute of Technology, 2013. http://hdl.handle.net/1853/47669.
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The very large number of distinct structures that are known for metal-organic frameworks (MOFs) and zeolites presents both an opportunity and a challenge for identifying materials with useful properties for targeted separations. In this thesis we propose a three-stage computational methodology for addressing this issue and comprehensively screening all available nanoporous materials. We introduce efficient pore size calculations as a way of discarding large number of materials, which are unsuitable for a specific separation. Materials identified as having desired geometric characteristics can be further analyzed for their infinite dilution adsorption and diffusion properties by calculating the Henry's constants and activation energy barriers for diffusion. This enables us to calculate membrane selectivity in an unprecedented scale and use these values to generate a small set of materials for which the membrane selectivity can be calculated in detail and at finite loading using well-established computational tools. We display the results of using these methods for >500 MOFs and >160 silica zeolites for spherical adsorbates at first and for small linear molecules such as CO₂ later on. In addition we also demonstrate the size of the group of materials this procedure can be applied to, by performing these calculations, for simple adsorbate molecules, for an existing library of >250,000 hypothetical silica zeolites. Finally, efficient methods are introduced for assessing the role of framework flexibility on molecular diffusion in MOFs that do not require defining a classical forcefield for the MOF. These methods combine ab initio MD of the MOF with classical transition state theory and molecular dynamics simulations of the diffusing molecules. The effects of flexibility are shown to be large for CH₄, but not for CO₂ and other small spherical adsorbates, in ZIF-8.
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Tian, Yuyang. "Synthesis and characterization of crystalline microporous materials : investigation of new synthetic routes." Thesis, University of St Andrews, 2014. http://hdl.handle.net/10023/6371.
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Conventionally, crystalline microporous materials such as zeolites and metal-organic frameworks (MOFs) are synthesized through the hydrothermal route or the trial-and-error approach. Other synthetic strategies may lead to the synthesis of microporous materials with new architectures or interesting properties. The general aim of this thesis is to investigate some new synthetic routes towards crystalline microporous materials. A top-down and post-synthesis method is reported in Chapter 4. Some zeolites are built up by layers and double-4-ring pillars. Germanium is preferentially located in the double-4-ring sites of a zeolite framework and is hydrolytically unstable. The idea of the top-down method is to disassemble these zeolites to the layer structures by dissolving the Ge-containing pillars and reassemble them to a new framework. This method is applied to the germanosilicate IWW and ITH zeolites for the first time. The effects of framework chemical compositions, Ge distributions and disassembling conditions on the top-down treatment process are investigated. The products obtained from the top-down treatment are characterised. An ionic liquid assisted strategy for the synthesis of zeolites is described in Chapter 5. The ionic liquid assisted strategy is a solvent free reaction. The raw materials are transformed to zeolites through a solid state reaction. The ionic liquids are first used as structure-directing agents (SDAs) in this solvent free reaction to replace the expensive quaternary ammonium hydroxide. A TON zeolite is synthesized using 1-ethyl-3-methylimidazolium bromide as the SDA. Moreover, the ionic liquid assisted strategy is considered as a “green chemistry” synthetic route due to the high yield of the zeolites and the minor production of waste water. Many aluminophosphates have been successfully synthesized through ionothermal routes. Most of them are synthesized using 1-alkyl-3-methylimidazolium based ionic liquids. A new ionic liquid, 1-(2-hydroxyl-ethyl)-3-methylimidazolium chloride ([HOEmim]Cl), is prepared and used for the ionothermal synthesis of aluminophosphate materials. A zeolite analogue with the CHA framework has been synthesized. At high synthetic temperatures, the products are large single crystals. The structures of the framework and the SDA are investigated by single crystal diffraction and other characterisation methods. Flexible MOF materials are usually synthesized by a trial-and-error approach. Recently a flexible MOF compound was synthesized using 5-sulfoisophthalic acid (SIP) as the ligand. It was proposed the sulfonate is weakly coordinated to the metal, which brings flexibility to the compound, and the carboxylate groups keep the framework intact. 2-sulfoterephthalic acid (STP) which also contains one sulfonate group and two carboxylate groups is believed to be an alternative ligand for the targeted synthesis of flexible MOFs. In Chapter 7, a MOF compound is synthesized using STP and 4, 4'-bipyridine (Bpy) as ligands to validate the proposed strategy can be generalized. Variable temperature single crystal diffraction analysis solves the structure and reveals a reversible structure transformation upon dehydration and rehydration.
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Gaillac, Romain. "Modélisation moléculaire des propriétés physico-chimiques de matériaux microporeux." Thesis, Paris Sciences et Lettres (ComUE), 2018. http://www.theses.fr/2018PSLEC005.
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Dans cette thèse, on réalise des études basées sur les méthodes de simulation numérique (Dynamique moléculaire ab initio notamment) des propriétés physico-chimiques des adsorbants cristallins utilisés industriellement, comme les zéolithes,ou qui pourraient l’être dans le futur, comme les matériaux hybrides MOFs (Metal–Organic Frameworks). On s’intéresse en premier lieu aux propriétés d’adsorption des fluides moléculaires et de leurs mélanges, mais aussi au comportement mécanique et thermique des solides nanoporeux. Il s'agit d'expliciter des relations structure-propriétés, par le biais de simulations multi-échelle, pour établir une véritable approche de design rationnel de tels matériaux<br>During this PhD, we perform studies based on numerical simulation (Ab initio molecular dynamics for instance) of physico-chemical properties for crystalline adsorbents industrially used, like zeolites,or could be used someday, like hybrid materials or MOFs (Metal–Organic Frameworks). We are primarily interested in adsorption properties of molecular fluids and their mixtures but also in the mechanical and thermal behaviors of nanoporous solids. The aim is to reveal relationships between molecular structures and properties, via multiscale modeling, to construct a rational design approach for such materials
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Bullot, Laetitia. "Elaboration de matériaux poreux et étude de leurs propriétés d'adsorption de dioxines/furanes." Thesis, Mulhouse, 2016. http://www.theses.fr/2016MULH9535/document.
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La protection de l’environnement et de la santé humaine représente une préoccupation éthique et scientifique primordiale. Les dioxines/furanes, produits, entre autres, par les processus d’incinération de déchets, font partie des polluants les plus dangereux de par leur stabilité et leur faculté à être bio-accumulés. Les polychlorobenzènes sont souvent référencés comme molécules modèles de ces composés et seront utilisés en tant que tels dans ces travaux de thèse. Grâce à leurs structures microporeuses organisées qui leur confèrent de remarquables capacités d’adsorption, les zéolithes et les Metal-Organic Frameworks (MOFs) représentent des matériaux de choix pour piéger ces polluants organiques. Leur mise en forme sous forme de billes par exemple offre l’avantage de s’affranchir de problèmes tels que le colmatage ou les pertes de charges trop importantes pouvant apparaître pour une application à l’échelle industrielle. C’est pourquoi, cette thèse vise à élaborer et caractériser des adsorbants zéolithiques et de type MOF, de les mettre en forme et d’étudier leurs propriétés d’adsorption vis-à-vis de polychlorobenzènes/dioxines/furanes. L’ensemble des zéolithes et MOFs ont été sélectionnés et préparés de sorte à optimiser leurs caractéristiques structurales, texturales et morphologiques pour les applications ciblées. Une étude sur la mise en forme de la zéolithe de type FAU a conduit à l’élaboration de billes présentant de bonnes propriétés mécanique et d’adsorption. Les différentes mesures d’adsorption de polychlorobenzènes/dioxines/furanes en phases gaz et liquide ont permis de mettre en évidence les meilleurs matériaux pour l’adsorption sélective de ces polluants à l’émission d’usines d’incinération de déchets<br>Environmental and human health protection is a scientific and ethical concern. Dioxin/furan compounds, produced from waste incineration process among other, are ones of the most dangerous pollutants due to their stability and ability to bio-accumulate. Polychlorobenzenes are often referred as model molecules of these compounds and will be used as it in this PhD work. Thanks to their microporous organized structures which confer to them remarkable adsorption capacities, zeolites and Metal-Organic Frameworks (MOFs) are interesting materials to trap these organic pollutants. Their shaping as beads for example offer the advantage to overcome problems such as clogging or excessive pressure losses that can appear for an industrial application. Therefore, the aim of this PhD is to prepare and characterize zeolite and MOF, to shape them and to study their adsorption properties for polychlorobenzenes/dioxins/furans. All zeolites and MOFs have been selected and prepared in order to optimize their structural, textural and morphological characteristics for the intended application. A study on the shaping of the FAU-type zeolite has allowed the development of beads with good mechanical and adsorption properties. The different polychlorobenzenes/dioxins/furans adsorption tests into gas and liquid phases allowed identifying the best solids for the selective adsorption of these pollutants in waste incineration plant emissions
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Boruntea, Cristian-Renato. "Design, synthesis and characterization of small-pore zeolites for industrial environmental applications." Doctoral thesis, Universitat Politècnica de València, 2020. http://hdl.handle.net/10251/141094.
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[ES] El Proyecto de investigación aquí descrito se estructura en dos partes. La primera parte se centra en la investigación fundamental con el objetivo de crear un protocolo para la síntesis de zeolitas. La segunda parte se refiere al diseño, síntesis y caracterización de nuevas zeolitas, particularmente utiles para aplicaciones DeNOx,, pero también podría ser útil para aplicaciones MTO.
La investigación fundamental sugiere un Nuevo modelo de preparación de zeolitas utilizando otras zeolitas como simiente. Este proceso se llama transformación zeolita-zeolita o también conversión interzeolita. El alto rendimiento obtenido, la rápida cristalización y la mejor utilización y rendimiento de los materiales de partida se han tenido en cuenta para mejorar el proceso en base a un proyecto de doctorado financiado por una empresa. Este método se ha ilustrado utilizando varias zeolitas como semilla, entre otras FAU y CHA, para la preparación de las dos zeolitas objetivo: AEI y AFX.
En la segunda parte, la investigación se centra en el diseño de nuevas zeolitas de poro medio. Se han seleccionado tres zeolitas hipotéticas de una base de datos de 933611 estructuras. Esta selección se ha realizado utilizando descriptores específicamente diseñados en base a la aplicabilidad de estas zeolitas en procesos DeNOx zeolitas. A continuación se han buscado los agentes directores de estructura (ADE) más apropiados, con la ayuda de métodos computacionales, algunos de los cuales se han sintetizado posteriormente. El uso de dichos ADE en el gel de síntesis ha permitido la obtención de una zeolita cuya topología (ERI) ha sido identificada mediante análisis por PXRD, y cuya morfología y tamaño de cristal (particularmente pequeño) la hacen muy adecuada para su uso como catalizador en algunos procesos.
El trabajo de síntesis también reveló la aparición de una nueva zeolita de alta densidad, llamada 'paracelsio-K'. Este nuevo material se ha obtenido al explorar el espacio de fases que cristalizan al utilizar 1-methyl-DABCO como ADE. La síntesis de esta zeolita tiene un especial interés porque el ADE no se incorpora en los canales de la zeolita, pero más bien influyendo en la nucleación y cristalización. La caracterización reveló que la composición del material es próxima al mineral microcline, estructuralmente cercano al paracelsio, ambos feldespatos. A diferencia de los feldespatos el paracelsio-K contiene moléculas de agua en su interior (1 molécula por cavidad) y puede describirse como el material más simple de la familia de las zeolitas que contiene cadenas del tipo 'doble-cigüeñal'. Utilizando los elementos topológicos correspondientes a esta estructura es posible generar estructuras zeolíticas ya conocidas, como GIS, APC, MER, PHI, SIV y algunas otras zeolitas hipotéticas.<br>[CAT] El Projecte d'investigació aquí descrit s'estructura en dos parts. La primera part se centra en la investigació fonamental amb l'objectiu de crear un protocol per a la síntesis de zeolites. La segona part es refereix al disseny, síntesis i caracterització de noves zeolites, particularment útils per a aplicacions DeNOx , però també podria ser útil per a aplicacions MTO.
La investigació fonamental suggereix un nou model de preparació de zeolites utilitzant altres zeolites com a llavor. Aquest procés s'anomena transformació zeolita-zeolita o també conversió interzeolita. L'alt rendiment obtingut, la ràpida cristal·lització i la millor utilització i rendiment dels materials de partida s'han tingut en compte per millorar el procés en base a un projecte de doctorat finançat per una empresa. Aquest mètode s'ha il·lustrat utilitzant diverses zeolites com a llavor, entre altres FAU i CHA, per a la preparació de les dues zeolites objectiu: AEI i AFX.
A la segona part, la investigació se centra en el disseny de noves zeolites de porus mitjà. S'han seleccionat tres zeolites hipotètiques d'una base de dades de 933.611 estructures. Aquesta selecció s'ha realitzat utilitzant descriptors específicament dissenyats sobre la base de l'aplicabilitat d'aquestes zeolites en processos DeNOx zeolites. A continuació s'han buscat els agents directors d'estructura (ADE) més apropiats, amb l'ajuda de mètodes computacionals, alguns dels quals s'han sintetitzat posteriorment.
L'ús d'aquests ADE al gel de síntesi ha permès l'obtenció d'una zeolita la topologia (ERI) ha estat identificada mitjançant anàlisi per PXRD, i la morfologia i mida de vidre (particularment petit) la fan molt adequada per al seu ús com a catalitzador en alguns processos. El treball de síntesi també va revelar l'aparició d'una nova zeolita d'alta densitat, anomenada 'paracelsio-K'. Aquest nou material s'ha obtingut a explorar l'espai de fases que cristal·litzen en utilitzar 1-methyl-DABCO com ADE. La síntesi d'aquesta zeolita té un especial interès perquè el ADE no s'incorpora en els canals de la zeolita, però més aviat influint en la nucleació i cristal·lització. La caracterització va revelar que la composició del material és propera al mineral microcline, estructuralment proper al paracelsio, tots dos feldspats. A diferència dels feldspats el paracelsio-K conté molècules d'aigua al seu interior (1 molècula per cavitat) i pot descriure com el material més simple de la família de les zeolites que conté cadenes del tipus 'doble-cigonyal'. Utilitzant els elements topològics corresponents a aquesta estructura és possible generar estructures zeolítiques ja conegudes, com GIS, APC, MER, PHI, SIV i algunes altres zeolites hipotètiques.<br>[EN] The research project described herein is structured in two parts. The first part is focused on the fundamental research with the aim of creating a toolbox for zeolite preparation. The second part deal with the design, synthesis and characterization of novel zeolites particular useful for DeNOx applications, but could be also useful for MTO applications.
The fundamental research is addressing a novel approach of preparing zeolites by using other zeolites as raw materials. This process is known as zeolite-to-zeolite transformation or interzeolite conversion. The high yield obtained, fast crystallization time and the better utilization of the raw materials (e.g. parent zeolite, organic structure directing agent (OSDA)), are important benefits of interzeolite conversion technic, which answer the objectives formulated for an industrial PhD project. The method has been exemplified by using various raw materials as parent zeolites, such as FAU and CHA for the preparation of two target small pore zeolites AEI and AFX.
In the second part the focus has been on the design of novel small pore zeolites. Three hypothetical frameworks have been selected by narrowing down a database containing 933611 structures. The selection has been performed by using the general descriptors for the state-of-the-art DeNOx zeolites (e.g. CHA). This was followed by finding suitable OSDAs for the selected frameworks, by using computational methods. The usage of the theoretically predicted OSDAs in synthesis gels made possible the synthesis of a novel high-silica zeolite. PXRD analysis, revealed that the zeolite has the ERI framework topology. The obtained material has a distinct particle morphology and smaller crystallites, which are key parameters for various catalytic processes.
The synthesis work revealed also a novel dense zeolite, named K-paracelsian. The new material has been obtained while exploring the phase space using 1-methyl-DABCO as OSDA. The synthesis of this zeolite is especially interesting in the sense that the OSDA is not being incorporated into the zeolite channels, but rather influencing the nucleation and crystallization. Further characterization revealed a material compositionally closely related to the mineral microcline and structurally closely related to the mineral paracelsian, both of which are feldspars. In contrast to the feldspars, K-paracelsian contains intrazeolitic water corresponding to one molecule per cage and can be described as the simplest endmember of a family of dense double-crankshaft zeolite topologies. By applying the identified building principle, a number of known zeolite frameworks (e.g. GIS, APC, MER, PHI, SIV) and hypothetical zeolite topologies can be constructed.<br>The authors thank Haldor Topsoe A/S and Innovation Fund Denmark for financial support under the
Industrial PhD programme (Case no. 1355-0174B). We thank MINECO of Spain for funding (SEV-2016-
0683 and RTI2018-101033-B-100) and ASIC-UPV for the use of computational facilities. We also thank
Prof. M. M. J. Treacy for assistance with the Database of Prospective Zeolite Structures.<br>Boruntea, C. (2020). Design, synthesis and characterization of small-pore zeolites for industrial environmental applications [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/141094<br>TESIS
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Domergue, Lionel. "Étude de la régénération d’adsorbants par oxydation indirecte." Thesis, Rennes 1, 2019. http://www.theses.fr/2019REN1S028.
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Du fait du coût élevé de certains matériaux adsorbants d’intérêt pour le traitement de la micropollution organique, l’étude a porté sur la régénération de matériaux adsorbants de type zéolithes hydrophobes et monolithe de carbone dans le cas de l’adsorption du bisphénol A et du diclofénac comme micropolluants réfractaires. Des procédés d’oxydation avancée impliquant des espèces radicalaires HO• (réaction de Fenton, électro-Fenton) et SO₄• – (activation de persulfate par voie thermique) ont été utilisés pour assurer la régénération des matériaux par désorption et dégradation oxydative des polluants fixés. La production de radicaux HO• au sein de la phase aqueuse circulant au niveau de l’adsorbant n’est pas suffisamment efficace pour sa régénération. Il a donc été envisagé de générer les radicaux au plus près des molécules adsorbées. Au cours de ce travail, une méthode sensible d’analyse par polarographie de H₂O₂ a été développée et validée pour le suivi des expériences avec les procédés mettant en jeu la réaction de Fenton. Pour différentes zéolithes, le catalyseur de la réaction de Fenton à base de fer a été incorporé préalablement dans la zéolithe. Pour le monolithe de carbone, les propriétés de conduction du matériau ont été mises à profit en l’utilisant comme cathode pour l’application du procédé électro-Fenton permettant de produire les radicaux HO• directement au sein du matériau. Cela a conduit à améliorer les performances de la régénération avec toutefois une diminution de son efficacité au cours de cycles successifs adsorption/régénération<br>The elimination of organic micropollutants often requires the use of adsorption processes among the water treatments. The aim of our study is to regenerate two expensive materials (hydrophobic zeolites and carbon monoliths) to increase their life expectancy and decrease their investing cost. Two organic contaminants were targeted : diclofenac and bisphenol A, which are refractory pollutants. Advanced oxidation processes involve radical species, HO• (Fenton and electro-Fenton reactions) and SO₄• – (thermal activation of persulfate ion). These oxidants were used to decompose the adsorbed pollutants and thus regenerate the adsorbents. The HO• production, within the core of aqueous phase, did not reach satisfactory regeneration, and a loss of adsorption capacity was observed. Furthermore, during this study, a sensitive polarographic analytical method was developed and validated for the quantification of H₂O₂ in the aqueous phase. This method was used to follow in situ the Fenton reaction. The location of the catalyst in a closer vicinity of the adsorbed species was then optimized and the iron catalyst was impregnated in the host, prior to the adsorption, on different types of hydrophobic zeolites. Concerning carbon monolith, the electro-Fenton process was carried out using the material as the cathode thanks to its electrical conductivity. Consequently, HO• are produced in the porosity of monolith. This latter property enhanced the degradation of adsorbed solutes. The overall performances were increased compared to the homogeneous Fenton process. Nonetheless, a decrease of the adsorption capacities with adsorption-regeneration cycles was observed
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ALCANTARA, RAQUEL R. "Síntese, caracterização, de nanomaterial zeolítico de cinzas de carvão organomodificado e aplicação como adsorvente na remediação de água contaminada por Rodamina B e Azul Direto 71." reponame:Repositório Institucional do IPEN, 2016. http://repositorio.ipen.br:8080/xmlui/handle/123456789/27960.
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Submitted by Marco Antonio Oliveira da Silva (maosilva@ipen.br) on 2017-10-27T12:15:25Z
No. of bitstreams: 0<br>Made available in DSpace on 2017-10-27T12:15:25Z (GMT). No. of bitstreams: 0<br>A síntese de zeólitas a partir de cinzas leves e pesadas de carvão mineral foi realizada por tratamento hidrotérmico alcalino, as quais foram nomeadas ZCL e ZCP, respectivamente. As zeólitas organomodificadas ZML e ZMP foram obtidas a partir da modificação superficial de ZCL e ZCP, respectivamente, utilizando o surfactante catiônico brometo de hexadeciltrimetilamônio. A partir das soluções remanescentes geradas na síntese de ZCL e ZCP foi possível sintetizar duas novas zeólitas. As características físicoquímicas dos nanomateriais zeolíticos sintetizados, bem como de suas respectivas matérias primas, tais como: capacidade de troca catiônica, massa específica, área específica, composição química, mineralógica e morfológica, entre outras, foram determinadas. Os adsorventes ZML e ZMP foram utilizados na remoção dos corantes Azul Direto 71 (DB71) e Rodamina B (RB) de soluções aquosas em sistema de batelada. Desta forma, quatro sistemas DB71/ZML, RB/ZML, DB71/ZMP e RB/ZMP foram investigados. Os modelos de pseudoprimeira ordem e pseudo-segunda ordem foram aplicados aos dados experimentais para o estudo da cinética de adsorção. O modelo de pseudosegunda ordem foi o que melhor descreveu o processo de adsorção de todos os sistemas corante/zeólita organomodificada. O equilíbrio da adsorção foi analisado a partir de quatro modelos de isoterma, sendo eles: Langmuir, Freundlich, Temkin e Dubinin-Radushkevich (D-R). Os resultados mostram que os modelos de Freundlich e Langmuir melhor descreveram os dados experimentais dos sistemas DB71/ZML e DB71/ZMP, respectivamente. Para os sistemas com RB, o modelo de D-R foi o que melhor se ajustou para ambos adsorventes ZML e ZMP. O planejamento fatorial 24 foi aplicado para a análise dos seguintes fatores que influenciam o processo de adsorção: concentração inicial do corante (Co), pH, dose de adsorvente (M) e temperatura (T). De acordo com as condições estudadas concluiu-se, com o intervalo de confiança igual a 95%, que para o sistema DB71/ZML, os fatores e suas interações que mais influenciam foram C0, M, pH, pH*M, pH*C0, M*C0, pH*M*C0, nessa ordem. No sistema DB71/ZMP, a ordem de influência foi: M, C0, pH, pH*M, pH*C0, M*C0, pH*M*C0. Para os sistemas RB/ZML e RB/ZMP, os resultados foram: M, C0, M*C0, pH, pH*M e M, C0, M*C0, respectivamente. O equilíbrio de adsorção foi atingido em cerca de 40 min para todas as amostras. As porcentagens de remoção do DB71 estavam na faixa de 50 80% e 20 50% para ZML e ZMP, respectivamente. A faixa de porcentagens de remoção do RB variou entre 60 80% e 30 50% para ZML e ZMP, respectivamente.<br>Dissertação (Mestrado em Tecnologia Nuclear)<br>IPEN/D<br>Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP
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Huh, Seong. "Morphological Control of Multifunctional Mesoporous Silica Nanomaterials for Catalysis Applications." Ames, Iowa : Oak Ridge, Tenn. : Ames Laboratory ; distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy, 2004. http://www.osti.gov/servlets/purl/837271-xREJ4t/webviewable/.
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Thesis (Ph.D.); Submitted to Iowa State Univ., Ames, IA (US); 19 Dec 2004.<br>Published through the Information Bridge: DOE Scientific and Technical Information. "IS-T 2397" Seong Huh. US Department of Energy 12/19/2004. Report is also available in paper and microfiche from NTIS.
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DISTEFANO, GAETANO. "Nanoporous dipeptide crystals as selective gas sorbents and polymerization nanovessels." Doctoral thesis, Università degli Studi di Milano-Bicocca, 2012. http://hdl.handle.net/10281/29103.
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Hydrophobic dipeptide crystals recently emerged as novel “organic zeolites” featuring tailorable pore size. In fact, seven out of nine pairwise combinations of L-isoleucine, L-valine and L-alanine amino acids crystallize according to the same charge-assisted hydrogen bond pattern, generating a family of microporous materials with right-handed 1D channels, having diameters in the sub-nanometer domain (<6Å), aliphatic environment and different degrees of helicity. The relationship between pore size and material properties was investigated with respect to gas separation, exploiting the affinity of carbon dioxide for the hydrophobic nanochannels of L-alanyl-L-valine (AV), L-isoleucyl-L-valine (IV) and L-valyl-L-isoleucine (VI). Reversible CO2 capture from an equimolar mixture of CO2 and methane, at room temperature and 1 atmosphere, was demonstrated with increasing purification performance with decrease in pore size. Dipeptide were also used as nanovessels in radical polymerizations with the aim of controlling otherwise non-specific reactions. Diene monomers (trans-1,3-pentadiene and isoprene) only yield linear 1,4-trans polymer in accordance with 1-dimensional pore geometry, while poly(acrylonitrile) (PAN) could be obtained as a stereoregular isotactic product by acrylonitrile polymerization in AV dipeptide. Finally, taking advantage of the dipeptide lability and unique thermal properties of poly(acrylonitrile), AV-PAN nanocomposites were used as a scaffold to obtain carbon replicas of the starting nanocomposite crystals (carbon micro-fibrils) showing anisotropic arrangement of the graphite domains.
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Ejaz, Tabassum. "Hydrothermal precipitation of zeolite-A crystals." Thesis, University College London (University of London), 1997. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.267693.
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Sarwar, Misbah. "Computer simulation of the adsorption of chlorinated organics in zeolites." Thesis, University College London (University of London), 2006. http://discovery.ucl.ac.uk/1445078/.
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Computer modelling techniques have been used to study the adsorption of three chlorinated hydrocarbons Dichloromethane, 1,2-Dichloroethane, and Trichloroethene in three different zeolite frameworks MFI, MOR and FAU. Calculations have been performed using both classical methods based on inter-atomic potentials, quantum mechanical Density Functional Theory (DFT) and combined QM/MM embedded methods. The first section of this thesis presents results of DFT calculations on purely siliceous and aluminosilicate gas-phase clusters. The results obtained are compared to experimental data and are found to differ significantly from experimental results. The reasons for this are rationalised and alternative methods suggested. The second section investigates some of these alternative approaches. Results of a Periodic DFT study and cluster calculations using a hybrid functional are presented. The QMPot embedded cluster method is then employed as an alternative to the cluster and periodic DFT approaches. The results of these different approaches are compared and rationalised. The thesis then moves on to describe atomistic simulations of the adsorption and diffusion of the molecules in the framework structures. The third section of this thesis uses the Grand Canonical Monte Carlo method to simulate adsorption isotherms and isosteric heat plots. The simulated data is found to be in good agreement to that in the literature. The final chapter describes results of a Molecular Dynamics simulation which models the diffusion of the molecules in the FAU framework at different temperatures.
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Bellet, Brice. "Synthèses de structurants organiques originaux pour la préparation de nouvelles structures zéolithiques." Thesis, Mulhouse, 2016. http://www.theses.fr/2016MULH8472/document.
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L’obtention de nouvelles structures zéolithiques a été permise grâce à la diversification des conditions de synthèse, comme l’utilisation d’ions fluorures, la substitution partielle du silicium par du germanium ou l’ajout d’un agent structurant organique. Les travaux développés au cours de cette thèse se concentrent sur la synthèse de nouveaux solides microporeux zéolithiques possédants de larges à extra-larges pores (>10 unités TO4) à l’aide de nouvelles molécules organiques structurantes. Le travail de thèse se divise donc en deux étapes avec, dans un premier temps, la synthèse de molécules organiques originales (dérivées de la pyrrolidine) qui sont ensuite engagées en synthèse hydrothermale. Huit nouveaux structurants non commerciaux ont été élaborés qui ont permis d'obtenir divers matériaux déjà connus, parmi lesquels les zéolithes octadécasil (AST), ITQ-7 (ISV), ITQ-17 (BEC) et ITQ-21. L'utilisation des cations N,N-diméthylperhydro-dicyclopenta[b,d]pyrrolium et N,N-diméthyldicyclopentylammon-ium, ont permis la découverte de deux nouveaux silicogermanates dont l’un de topologie connue nommé clovérite (-CLO) et l’autre nommé Mu-43 présentant une topologie de charpente inédite. Chacun de ces deux matériaux possède un système tridimensionnel de canaux avec des ouvertures à 12 atomes T (Mu-43) ou à 20 atomes T (clovérite)<br>Several synthetic strategies have emerged such as the use of fluoride, the introduction of germanium and the development of new organic structure directing agents (SDAs) to obtain zeolites, which have led to significant structural diversity. Previous works at the laboratory enable us to develop a new range of non-commercial SDAs that have been designed to produce novel extra-large pores zeolites (>10 TO4 units). Elaborated organic structure directing agents (pyrrolidine derivatives) were first synthesized by a concise route and then engaged in hydrothermal synthesis. Eight non-commercial and original SDAs were produced which led to the synthesis of several known zeolites such as octadecasil (AST), ITQ-7 (ISV), ITQ-17 (BEC) and ITQ-21. The use of the cations N,N-dimethylperhydro-dicyclopenta[b,d]pyrrolium and N,N-dimethyldicyclopentyl-ammonium, allowed us to discover two new silicogermanates named cloverite of known topology -CLO and the novel one Mu 43. Each of these two materials possesses a three-dimensional channel system with 12-membered ring pores (Mu-43) or 20-membered ring pores (cloverite)
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Wollmann, Philipp, Matthias Leistner, Ulrich Stoeck, et al. "High-throughput screening: speeding up porous materials discovery." Saechsische Landesbibliothek- Staats- und Universitaetsbibliothek Dresden, 2014. http://nbn-resolving.de/urn:nbn:de:bsz:14-qucosa-138648.
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A new tool (Infrasorb-12) for the screening of porosity is described, identifying high surface area materials in a very short time with high accuracy. Further, an example for the application of the tool in the discovery of new cobalt-based metal–organic frameworks is given<br>Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich
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Chretien, Michelle N. "Photochemical, photophysical, and photobiological studies of zeolite guest-host complexes." Thesis, University of Ottawa (Canada), 2005. http://hdl.handle.net/10393/29205.
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This thesis focuses on the photochemistry and photophysics of a variety of zeolite complexes, from catalysts to sunscreens. The first chapter describes the preparation and photophysical and photochemical characterization of two new photocatalytic materials. The catalysts are based on a multi-component zeolite, host-guest complex and the interaction between components was probed using time-resolved spectroscopic techniques. The catalytic efficiency, in terms of the ability to photodegrade biological contaminants, was also investigated. These studies were performed with the aim of developing efficient catalysts for wastewater remediation which can be used with solar (visible) radiation.
In subsequent chapters, zeolite materials have been used as matrices for the stabilization of various transient or reactive species. In the case of ZSM-5-type zeolite, the dibenzotropylium cation was rendered indefinitely persistent allowing the examination of its excited-state behaviour. The geometric restriction within the cavities also permits the observation of electron transfer chemistry in the absence of a nucleophilic addition reaction with the electron donor. In a second example, ketoprofen (a non-steroidal anti-inflammatory drug) was found to undergo intrazeolite photodecarboxylation to generate a benzylic carbanion. The lifetime of the zeolite-encapsulated carbanion was found to be fifty times longer than in solution. The enhanced lifetime allows intermolecular nucleophilic addition chemistry to compete with protonation, effectively, a photo-initiated Grignard-type reaction is observed.
In Chapter 6, fluorescence is used as tool to probe both intra- and interzeolite interactions. In the first part, a zeolite-entrapped radical probe was prepared by ship-in-a-bottle synthesis for the investigation of radical percolation in the zeolite matrix. The probe is a molecular dyad containing a persistent free-radical and a quenched fluorophore. When the probe radical couples with a carbon-centered radical, the probe fluorescence is restored and in this way free-radical species in heterogeneous systems can be conveniently examined. In the second section, zeolite particles were irreversibly labeled with a biologically-compatible fluorophore (also by ship-in-a-bottle synthesis).
The last part of this thesis deals with a project relating to supramolecular sunscreens. (Abstract shortened by UMI.)
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Kabalan, Ihab. "Synthèse des matériaux nanoporeux pour la décontamination moléculaire et le stockage d'énergie." Thesis, Mulhouse, 2016. http://www.theses.fr/2016MULH9073/document.
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Les composés organiques volatiles (COVs) sont les polluants organiques atmosphériques les plus abondants. Parmi les différentes solutions pour combattre cette pollution, l'utilisation d'adsorbants moléculaires tels que les zéolithes semble être efficace. Cependant les synthèses classiques de zéolithes aboutissent généralement à des tailles de cristaux de l'ordre de plusieurs dizaines de micromètres. Les capacités et les cinétiques de piégeage, sensibles aux phénomènes de diffusion et de surface pourraient potentiellement être améliorées par l'utilisation de nanocristaux ou de produits zéolithiques hiérarchisés (micro/mésoporeux). Dans ce travail de thèse, nous avons synthétisé des zéolithes aluminosiliciques ou purement siliciques de type structural FAU, MFI et *BEA. Ces dernières sont synthétisées avec différentes morphologies et tailles de particules telles que les nanocristaux et les zéolithes hiérarchisées (nanofeuillets et/ou nanoéponges en utilisant des agents structurants bifonctionnels). Ces matériaux sont comparés aux zéolithes conventionnelles, afin d'étudier l'influence de la morphologie sur la cinétique et la capacité de piégeage de COVs. Les caractéristiques structurales et texturales des zéolithes synthétisées ont été étudiées par ORX, MEB, manométrie d'adsorption/désorption de diazote, ATG-ATD, RMN du solide. Enfin, la capacité d'adsorption d'une molécule modèle, le n-hexane, au sein de ces zéolithes a été étudiée par thermogravimétrie. Dans le cas des zéolithes de type MFI et *BEA, les zéolithes hiérarchisées ont montré une augmentation de la capacité de piégeage en n-hexane par rapport aux zéolithes conventionnelles. La capacité de piégeage en n-hexane a été multipliée par 7 dans le cas des nanoéponges de type *BEA et par 6 dans le cas des nanocristaux de type *BEA comparés aux microcristaux de type *BEA (693 mg/g vs 103 mg/g et 591 mg/g vs 103 mg/g, respectivement)<br>Volatile organic compounds (VOCs) are the most abundant organic pollutants. Among the various solutions to fight against this pollution, the use of molecular adsorbents appears as a potential alternative for the control of contamination. The porous materials have many advantages due to their low cost, their physical characteristics and their useful properties related to their structure and their large surface area. However, conventional synthesis of zeolites generally lead to micrometer size crystals. The capacity and the kinetics of adsorption that are sensitive to the diffusion and the surface phenomena could be potentially improved by the use of zeolite nanocrystals or hierarchical products (micro / mesoporous). These nanomaterials have high potential due to their small size and their exalted outer surface that promote access of pollutants and improve the adsorption capacity. ln the thesis work, we synthesized zeolites with different structural types such as FAU, MFI and *BEA. Each structure type was synthesized in different morphologies such as nanosponges and /or nanosheets using a bifunctional structuring agent, as well as nanocrystals by the clear solution method. These materials were compared with conventional micrometer-sized zeolites. The purity and the porous texture have been characterized by using XRD, SEM, nitrogen adsorption/desorption techniques, TGA-DTA and solid state NMR. Finally, the adsorption capacity of a model molecule, the n-hexane, in these zeolites have been studied by thermogravimetry. In the case of *BEA and MFI-type zeol ites, the hierarchical zeolites showed an increase of the adsorption capacity of n-hexane compared to conventional zeolites. The adsorption capacity of n-hexane was multiplied by 7 in the case of *BEA-type nanosponges and by 6 in the case of the *BEA-type nanocrystals compared to *BEA_type microcrystals (693 mg / g vs 103 mg / g and 591 mg / g vs 103 mg / g, respectively)
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Gräser, Annett. "Kationische Wirt-Gast-Polymerisation in Y-Zeolithen und MCM-41 Synthese und Charakterisierung neuartiger organisch-anorganischer Polymer-Zeolith-Hybride /." [S.l. : s.n.], 2000. http://deposit.ddb.de/cgi-bin/dokserv?idn=963255681.
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Gräser, Annett. "Kationische Wirt-Gast-Polymerisation in Y-Zeolithen und MCM-41: Synthese und Charakterisierung neuartiger organisch-anorganischer Polymer-Zeolith-Hybride." Doctoral thesis, Universitätsbibliothek Chemnitz, 2000. http://nbn-resolving.de/urn:nbn:de:bsz:ch1-200000522.
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Die Synthese von neuartigen organisch-anorganischen Polymer-Zeolith-Hybriden wird in der vorliegenden Arbeit vorgestellt. Die Hybride wurden durch kationische Polymerisation elek-tronenreicher Monomere direkt in den Poren der Zeolithe und zeolithanalogen Materialien hergestellt. Die Vinylether Ethyl-, Isobutyl-, Cyclohexyl- und 2-Chlor-ethylvinylether, 2,3-Dihydrofuran, 2-Methoxypropen sowie N-Vinylcarbazol wurden zur Herstellung der orga-nischen Komponente der Hybride genutzt. Die Polymerisation wurde dabei einerseits durch die Protonen der Zeolithgitter und andererseits durch separate Oberflächeninitiatoren gestar-tet. Die anorganische Basis der Hybride bildeten vorrangig mikroporöser HY-Zeolith und mesoporöses MCM-41.
Bei der Synthese entstand neben dem eingeschlossenen Polymer im Zeolith eine vom Hybrid extrahier-bare Polymerfraktion. Beide Fraktionen wurden mittels GPC und einer speziellen Kopplung von GPC und UV/Vis-Spektrometer analysiert. DSC und dielektrische Spektro-skopie wurden zur Glasübergangstemperaturbestimmung herangezogen.
Die Strukturuntersuchung der neuartigen Hybridmaterialien erfolgte mit Festkörper-NMR-Spektroskopie, Röntgendiffraktometrie XRD, Transmissionselektronenmikroskopie TEM, Sekun-därelektro-nenmikroskopie SEM, Elektronenstrahlmikroanalyse ESMA, UV/Vis-Spektroskopie und Infrarotspektroskopie FT-IR. Die Porentopologie wurde mit Stick-stoff-sorp-tionsmessungen bestimmt.
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Wollmann, Philipp, Matthias Leistner, Ulrich Stoeck, et al. "High-throughput screening: speeding up porous materials discovery." Royal Society of Chemistry, 2011. https://tud.qucosa.de/id/qucosa%3A27767.
Full textAbstract:
A new tool (Infrasorb-12) for the screening of porosity is described, identifying high surface area materials in a very short time with high accuracy. Further, an example for the application of the tool in the discovery of new cobalt-based metal–organic frameworks is given.<br>Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.
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Stevens, Adrian Philip. "Computational investigations of the role of organic templating agents in zeolite synthesis." Thesis, University of Portsmouth, 1996. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.481665.
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In this thesis, a number of molecular modelling techniques have been used to investigate the role of organic templating agents in the synthesis of zeolite microporous materials. Initially, molecular similarity tools were applied in order to investigate trends in the structural properties of templates. The results highlighted a strong correlation, showing that templates which facilitate the synthesis of the same zeolite, share similar dimensions. Subsequent manual docking studies, based on molecular graphics have helped to provide an insight into the basis for the observed relationships, revealing a close match between the dimensions of the templates and the topology of the channel systems of the microporous materials. A combined Monte Carlo / Simulated Annealing protocol was developed to predict in a rigorous manner, the location and orientation adopted by templates within periodic models of the host frameworks. This approach revealed that in addition to a strong shape-based relationship between template and zeolite, a further correlation was exhibited between templates, in the form of a `sub-shape' phenomena in the packing arrangements adopted within the microporous structures. In terms of the `Templating' theory of zeolite synthesis, this helped to rationalise previous experimental work which showed that some template molecules could facilitate the synthesis of more than one zeolite and also that some zeolites could be synthesised from a wide range of templates. Finally, a mechanism is proposed, linking template packing arrangements to extended defect stacking faults in two zeolite materials, Beta and NU-86.
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Mbafor, William Fru. "Synthesis, characterisation and application of zeolite titanium (Al) beta in organic transformations." Thesis, University of Liverpool, 2000. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.367145.
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DAVYDOV, LEV. "PHOTOCATALYTIC DEGRADATION OF ORGANIC CONTAMINANTS: NOVEL CATALYSTS AND PROCESS." University of Cincinnati / OhioLINK, 2001. http://rave.ohiolink.edu/etdc/view?acc_num=ucin995381776.
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Wang, Nanyi [Verfasser]. "Zeolite and metal-organic framework membranes for pervaporation and gas separation / Nanyi Wang." Hannover : Technische Informationsbibliothek und Universitätsbibliothek Hannover (TIB), 2015. http://d-nb.info/1071668943/34.
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Cosseron, Anne-Flore. "Evaluation et traitement des polluants émis par un moteur thermique fonctionnant avec des biocarburants." Phd thesis, Université de Haute Alsace - Mulhouse, 2012. http://tel.archives-ouvertes.fr/tel-00860233.
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Les biocarburants présentent une alternative prometteuse à l'utilisation de carburants fossiles. Cependant, l'augmentation de la quantité de biocarburants introduite dans les carburants nécessite de connaître leur impact sur les émissions de polluants. Le travail réalisé lors de cette thèse peut être décrit en deux parties : La première traite de l'évaluation des émissions de polluants réglementés et non réglementés émis par la combustion de biocarburants dans un moteur diesel. Différents biocarburants ont été testés : des esters méthyliques d'huile de soja et de colza, des esters éthyliques d'huile usagée et un carburant de référence exempt de tout biocarburant. Les résultats montrent que la nature des biocarburants ainsi que leur teneur ont un impact sur les polluants émis. Par exemple, une diminution de la taille des particules émises a été observée avec l'utilisation des esters méthyliques d'huile de soja. Le deuxième objectif de cette thèse concerne le piégeage des polluants Diesel, notamment des composés organiques volatils par des zéolithes. Plusieurs zéolithes ont été synthétisées puis caractérisées. Des tests d'adsorption par thermogravimétrie ont ensuite été réalisés au laboratoire avec différentes molécules sondes représentatives des polluants émis par les moteurs Diesel (le n-hexane, le p-xylène et l'acétone). Certaines zéolithes comme les zéolithes faujasite présentent des capacités d'adsorption intéressantes. Toutefois, la plupart des résultats montrent une diminution de la capacité d'adsorption avec l'augmentation de la température. Ces zéolithes ont ensuite été placées en sortie d'échappement d'un moteur diesel afin d'étudier leur capacité d'adsorption.
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Chihara, Kazuyuki, Takashi Matsumoto, and Kazunori Hijikata. "Azeotropic adsorption of organic solvent vapor mixture on high silica zeolite, mass transfer dynamics." Universitätsbibliothek Leipzig, 2016. http://nbn-resolving.de/urn:nbn:de:bsz:15-qucosa-194773.
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Dede, Ozlem. "Pervaporation Of Organic/water Mixtures By Mfi Type Zeolite Membranes Synthesized In A Flow System." Master's thesis, METU, 2007. http://etd.lib.metu.edu.tr/upload/12608646/index.pdf.
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Zeolite membrane synthesis is conventionally carried out in batch systems. Recently, several
attempts have been performed to synthesize zeolite membranes in flow systems which can
allow preparation of membranes with large specific surface areas.
Membranes synthesized in the recirculating flow system had comparable N2/SF6 and n-
C4H10/i-C4H10 ideal selectivities with the membranes prepared in the batch system, indicating
that good quality membranes can be produced by this method. The objective of this study is to
separate organic/water mixtures by pervaporation by using MFI type membranes synthesized
in the flow system. Effect of number of synthesis steps and synthesis method on the
separation factor and flux was investigated.
Membranes were synthesized from clear solutions with a molar composition of
80SiO2:16TPAOH:1536H2O at 95oC and atmospheric pressure. The synthesis solution was recirculated through the tubular alumina support with a flow rate of 6 ml/min for 72 h. The
membranes were characterized by X-ray diffraction for phase identification and scanning
electron microscopy for morphology determination. Single gas permeances of N2, H2, CH4,
CO2, n-C4H10 and i-C4H10 were measured between 25 and 200oC. Mixtures of 5 wt%
ethanol/water, 2-propanol/water and acetone/water were separated by pervaporation at
different temperatures.
The single gas permeances decreased with increasing temperature for weakly adsorbed gases.
For n-C4H10 the permeance passed through a maximum and i-C4H10 permeance was nearly
constant. For a membrane synthesized by two consecutive synthesis steps, the ideal
selectivity for n-C4H10/i-C4H10 was 132 at 200oC. The selectivity in the pervaporation
separation of ethanol-water mixture was 43 with a permeate flux of 0.2 kg/m2h at 25oC. With
increasing temperature, selectivity decreased but the flux increased, the selectivity was 23 and
the flux was 1.9 kg/m2h at 85oC. 2-propanol/water and acetone/water separation factors were
36 and 1024 with 0.2 and 0.1 kg/m2h fluxes, respectively. The separation factors and fluxes
for membranes synthesized in the flow system were comparable with membranes synthesized
in the batch system.
48
Topolniak, Ievgeniia. "Photodegradation of polymer nanocomposites for encapsulation of organic solar cells." Thesis, Clermont-Ferrand 2, 2015. http://www.theses.fr/2015CLF22630.
Full textAbstract:
L'objectif de ce travail était le développement des nanocomposites d’EVOH/zeolites à base de charges telles que les zéolites pour l’encapsulation des cellules solaires organiques, et l’étude de leur comportement photochimique. Ce travail a porté sur l’étude du mécanisme de photooxydation des copolymères d’EVOH puis sur l'impact des zéolites sur ce mécanisme. Les propriétés fonctionnelles des nanocomposites d’EVOH/zéolites ont été étudiées en prenant en compte le taux de charge et la taille des particules. Les propriétés des copolymères d’EVOH et des nanocomposites d’EVOH/zéolites comme la transparence optique, la morphologie de surface, les propriétés mécaniques et thermiques, et les propriétés d'absorption de l'eau ont été étudiées. Sur la base des résultats obtenus, les meilleurs candidats pour l'encapsulation des cellules solaires organiques ont été proposés. Le mécanisme de photooxydation des copolymères a été proposé, la photostabilité des matériaux et l'impact des zéolites sur le comportement photochimique du polymère ont été étudiés. Le test électrique de calcium et le suivi des performances des cellules solaires organiques encapsulées ont été effectués afin d'évaluer l’efficacité des matériaux étudiés comme candidats potentiels pour une encapsulation efficace et stable des cellules solaires<br>The goal of this work was to develop EVOH/zeolite nanocomposites based on inorganic fillers such as zeolites for potential encapsulation of OSCs and to investigate their photochemical behaviour. The research was focused on the photooxidation mechanism of pristine EVOH copolymers and on the impact of the filler addition on this mechanism. EVOH/zeolite nanocomposites functional properties were characterised taking into account different particle sizes and filler contents. Properties of EVOH copolymers and EVOH/zeolites nanocomposites such as optical transparency, surface morphology, mechanical and thermal properties, and water uptake properties were investigated. On the basis of obtained results, the best candidate(s) for encapsulation of organic solar cells has been proposed. The chemical degradation mechanism of pristine polymers has been proposed, the materials photostability and the impact of the zeolite particles on the photochemical behaviour of the polymer have been studied. Electrical calcium test and performance of encapsulated OSCs were carried out in order to evaluate the ability of the studied materials to be used as potential candidates for efficient and stable encapsulation coatings for OSCs applications
49
Akinsiku, Sileola B. "Detecting Organic Molecules on the Surface of Inorganic Dust Particles Using Aerosol Mass Spectrometry." DigitalCommons@USU, 2009. https://digitalcommons.usu.edu/etd/369.
Full textAbstract:
Detection of organic molecules present on the surface of dust particles is important in homeland security, agriculture, and several other applications. The research presented reports the ability of the aerosol mass spectrometer (AMS) to detect molecules on the surface of dust particles without detecting the particle core. Experiments were carried out to detect semi-volatile organic compounds adsorbed onto the surface of particulates without interference from the dust particle core. Methyl salicylate, oleic acid, and organophosphorus pesticides such as Malathion were detected on the surface of particles representative of dust-type materials. Zeolite powders were used as aerosol support, representative of a typical silica mineral aerosol present in the atmosphere. Mass spectral fingerprint information was gained by first directly detecting atomized species to record their clean electron impact mass spectrum. This facilitated detection during later experiments of organic molecules coated on an inorganic support. Spectra obtained give mass spectrometric signatures of molecules coated on inorganic particles without detection of the particle core. An important feature of the AMS is the ability to equate an ion rate detected in the mass spectrometer to a mass concentration of a given chemical species in a sample using its ionization efficiency. Based on an average inlet flow rate of 1.2 cm 3sec -1 the ionization efficiencies obtained were 5.89x10-5, 1.15x10-6, and 1.62x10-5 for Malathion, methyl salicylate, and oleic acid, respectively. These experiments and the results obtained show that detection and characterization of organic species adsorbed onto inorganic dust particles are possible at µg m-3 concentrations using the AMS.
50
Abdelhamid, Hani Nasser. "Lanthanide Metal-Organic Frameworks and Hierarchical Porous Zeolitic Imidazolate Frameworks : Synthesis, Properties, and Applications." Doctoral thesis, Stockholms universitet, Institutionen för material- och miljökemi (MMK), 2017. http://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-146398.
Full textAbstract:
This thesis presents the synthesis, properties, and applications of two important classes of metal-organic frameworks (MOFs); lanthanide MOFs and hierarchical porous zeolitic imidazolate frameworks (ZIFs). The materials have been characterized using a wide range of techniques including diffraction, imaging, various spectroscopic techniques, gas sorption, dynamical light scattering (DLS) and thermogravimetric analysis (TGA). In Chapter 1, the unique features of MOFs and ZIFs as well as their potential applications are summarized. In Chapter 2, different characterization techniques are presented. Chapter 3 describes a family of new isoreticular lanthanide MOFs synthesized using tri-topic linkers of different sizes, H3L1-H3L4, denoted SUMOF-7I-IV (Ln) (SU; Stockholm University, Ln = La, Ce, Pr, Nd, Sm, Eu and Gd, Paper I). The SUMOF-7I-III (Ln) contain permanent pores and exhibit exceptionally high thermal and chemical stability. The luminescence properties of SUMOF-7IIs are reported (Paper II). The influences of Ln ions and the tri-topic linkers as well as solvent molecules on the luminescence properties are investigated. Furthermore, the potential of SUMOF-7II (La) for selective sensing of Fe (III) ions and the amino acid tryptophan is demonstrated (Paper III). Chapter 4 presents a simple, fast and scalable approach for the synthesis of hierarchical porous zeolitic imidazolate framework ZIF-8 and ZIF-67 using triethylamine (TEA)-assisted approach (Paper IV). Organic dye molecules and proteins are encapsulated directly into the ZIFs using the one-pot method. The photophysical properties of the dyes are improved through the encapsulation into ZIF-8 nanoparticles (Paper IV). The porosity and surface area of the ZIF materials can be tuned using the different amounts of dye or TEA. To further simplify the synthesis of hierarchical porous ZIF-8, a template-free approach is presented using sodium hydroxide, which at low concentrations induces the formation of zinc hydroxide nitrate nanosheets that serve as in situ sacrificial templates (Chapter 5, Paper V). A 2D leaf-like ZIF (ZIF-L) is also obtained using the method. The hierarchical porous ZIF-8 and ZIF-L show good performance for CO2 sorption.<br><p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 2: Manuscript. Paper 5: Manuscript.</p>