Vers l’identification d’inhibiteurs de croissance pour la synthèse de cristaux de zéolithes de taille nanométrique

Zeolites are widely used in catalysis. One of today’s major challenges is to obtain nanometer-sized crystals, offering promising prospects for the design of more active and more selective acid catalysts, in particular for heavy oil conversion processes. Zeolite nanocrystals can be obtained by using growth inhibitors. This thesis focused on the identification of two families of organic compounds limiting the crystals growth. For the first one, the growth inhibition is favored by the adsorption of organic compounds (polycations, amino acids…) on the surface of growing crystals. This study was conducted using a high-throughput experiment methodology and led to zeolite Y (FAU) crystals of 300 nm by the addition of L-lysine. The second family is derived from Ryoo’s team approach and consists of the use of bifunctional compounds including one structure-directing function and one growth-inhibiting function. This study started with the synthesis of MFI zeolite. The molecular modelling allowed identifying an alkyl mono-ammonium directing the formation of 2 nm-thick nanosheets of zeolite ZSM-5. The kinetic study revealed that this zeolite is synthesized from a lamellar polysilicate formed in situ. This identification strategy, coupled to a high-troughput experiment methodology, was applied to the synthesis of zeolites EMC-1 (FAU) and EMC-2 (EMT) and conducted to the elaboration of new structure-directing agents and their bifunctional counterparts.Les zéolithes sont largement utilisées en catalyse. Un enjeu majeur est d'obtenir des cristaux nanométriques qui offrent des perspectives prometteuses dans la conception de catalyseurs acides plus actifs et plus sélectifs, notamment pour les procédés de conversion des coupes lourdes pétrolières. L'obtention de ces nano-cristaux peut résulter de l'utilisation d'inhibiteurs de croissance. Cette thèse s'est attachée à identifier deux familles de composés organiques limitant la croissance des cristaux. Pour la première, l'inhibition est envisagée par adsorption de composés organiques (polycations, acides aminés...) sur la surface des cristaux en formation. Cette étude a été réalisée en suivant une méthodologie d'expérimentation à haut-débit et a conduit à des cristaux de zéolithe Y (FAU) de 300 nm par l'ajout de L-lysine. La seconde famille est dérivée de l’approche de l’équipe de Ryoo et consiste en l’utilisation de composés bifonctionnels comportant une fonction structurante et une fonction inhibitrice de croissance. Cette étude a démarré par la synthèse de zéolithe MFI. La modélisation moléculaire a permis d'identifier un mono-ammonium alkylé favorisant la formation de nanofeuillets de zéolithe ZSM-5 d'épaisseur voisine de 2 nm. L'étude cinétique a révélé par ailleurs que cette zéolithe est synthétisée à partir d’un polysilicate lamellaire formé in situ. Cette stratégie d'identification, couplée à une méthodologie d'expérimentation à haut débit, a alors été appliquée à la synthèse des zéolithes EMC-1 (FAU) et EMC-2 (EMT), et a conduit à l'élaboration de nouveaux agents structurants et composés bi-fonctionnels

Systematic study of the impact of MOF densification into tablets on textural and mechanical properties

Four different metal-organic framework powders (UiO-66, UiO-66-NH, UiO-67, and HKUST-1) were shaped into tablets. The effect of the applied pressure on porous properties, mechanical resistance and tablet bulk density is reported. We observe a linear relationship between densification and tensile strength for all four studied MOFs, with the slope being MOF-dependent. We also report conditions for improving significantly the volumetric uptake. Finally, we evaluated our tablets' stability over time in the presence of moisture

Toward the identification of growth inhibitors for the synthesis of nano-sized zeolite crystals

Les zéolithes sont largement utilisées en catalyse. Un enjeu majeur est d'obtenir des cristaux nanométriques qui offrent des perspectives prometteuses dans la conception de catalyseurs acides plus actifs et plus sélectifs, notamment pour les procédés de conversion des coupes lourdes pétrolières. L'obtention de ces nano-cristaux peut résulter de l'utilisation d'inhibiteurs de croissance. Cette thèse s'est attachée à identifier deux familles de composés organiques limitant la croissance des cristaux. Pour la première, l'inhibition est envisagée par adsorption de composés organiques (polycations, acides aminés...) sur la surface des cristaux en formation. Cette étude a été réalisée en suivant une méthodologie d'expérimentation à haut-débit et a conduit à des cristaux de zéolithe Y (FAU) de 300 nm par l'ajout de L-lysine. La seconde famille est dérivée de l’approche de l’équipe de Ryoo et consiste en l’utilisation de composés bifonctionnels comportant une fonction structurante et une fonction inhibitrice de croissance. Cette étude a démarré par la synthèse de zéolithe MFI. La modélisation moléculaire a permis d'identifier un mono-ammonium alkylé favorisant la formation de nanofeuillets de zéolithe ZSM-5 d'épaisseur voisine de 2 nm. L'étude cinétique a révélé par ailleurs que cette zéolithe est synthétisée à partir d’un polysilicate lamellaire formé in situ. Cette stratégie d'identification, couplée à une méthodologie d'expérimentation à haut débit, a alors été appliquée à la synthèse des zéolithes EMC-1 (FAU) et EMC-2 (EMT), et a conduit à l'élaboration de nouveaux agents structurants et composés bi-fonctionnels.Zeolites are widely used in catalysis. One of today’s major challenges is to obtain nanometer-sized crystals, offering promising prospects for the design of more active and more selective acid catalysts, in particular for heavy oil conversion processes. Zeolite nanocrystals can be obtained by using growth inhibitors. This thesis focused on the identification of two families of organic compounds limiting the crystals growth. For the first one, the growth inhibition is favored by the adsorption of organic compounds (polycations, amino acids…) on the surface of growing crystals. This study was conducted using a high-throughput experiment methodology and led to zeolite Y (FAU) crystals of 300 nm by the addition of L-lysine. The second family is derived from Ryoo’s team approach and consists of the use of bifunctional compounds including one structure-directing function and one growth-inhibiting function. This study started with the synthesis of MFI zeolite. The molecular modelling allowed identifying an alkyl mono-ammonium directing the formation of 2 nm-thick nanosheets of zeolite ZSM-5. The kinetic study revealed that this zeolite is synthesized from a lamellar polysilicate formed in situ. This identification strategy, coupled to a high-troughput experiment methodology, was applied to the synthesis of zeolites EMC-1 (FAU) and EMC-2 (EMT) and conducted to the elaboration of new structure-directing agents and their bifunctional counterparts

Vers l'identification d'inhibiteurs de croissance pour la synthèse de cristaux de zéolithes de taille nanométrique

Les zéolithes sont largement utilisées en catalyse. Un enjeu majeur est d'obtenir des cristaux nanométriques qui offrent des perspectives prometteuses dans la conception de catalyseurs acides plus actifs et plus sélectifs, notamment pour les procédés de conversion des coupes lourdes pétrolières. L'obtention de ces nano-cristaux peut résulter de l'utilisation d'inhibiteurs de croissance. Cette thèse s'est attachée à identifier deux familles de composés organiques limitant la croissance des cristaux. Pour la première, l'inhibition est envisagée par adsorption de composés organiques (polycations, acides aminés...) sur la surface des cristaux en formation. Cette étude a été réalisée en suivant une méthodologie d'expérimentation à haut-débit et a conduit à des cristaux de zéolithe Y (FAU) de 300 nm par l'ajout de L-lysine. La seconde famille est dérivée de l approche de l équipe de Ryoo et consiste en l utilisation de composés bifonctionnels comportant une fonction structurante et une fonction inhibitrice de croissance. Cette étude a démarré par la synthèse de zéolithe MFI. La modélisation moléculaire a permis d'identifier un mono-ammonium alkylé favorisant la formation de nanofeuillets de zéolithe ZSM-5 d'épaisseur voisine de 2 nm. L'étude cinétique a révélé par ailleurs que cette zéolithe est synthétisée à partir d un polysilicate lamellaire formé in situ. Cette stratégie d'identification, couplée à une méthodologie d'expérimentation à haut débit, a alors été appliquée à la synthèse des zéolithes EMC-1 (FAU) et EMC-2 (EMT), et a conduit à l'élaboration de nouveaux agents structurants et composés bi-fonctionnels.Zeolites are widely used in catalysis. One of today s major challenges is to obtain nanometer-sized crystals, offering promising prospects for the design of more active and more selective acid catalysts, in particular for heavy oil conversion processes. Zeolite nanocrystals can be obtained by using growth inhibitors. This thesis focused on the identification of two families of organic compounds limiting the crystals growth. For the first one, the growth inhibition is favored by the adsorption of organic compounds (polycations, amino acids ) on the surface of growing crystals. This study was conducted using a high-throughput experiment methodology and led to zeolite Y (FAU) crystals of 300 nm by the addition of L-lysine. The second family is derived from Ryoo s team approach and consists of the use of bifunctional compounds including one structure-directing function and one growth-inhibiting function. This study started with the synthesis of MFI zeolite. The molecular modelling allowed identifying an alkyl mono-ammonium directing the formation of 2 nm-thick nanosheets of zeolite ZSM-5. The kinetic study revealed that this zeolite is synthesized from a lamellar polysilicate formed in situ. This identification strategy, coupled to a high-troughput experiment methodology, was applied to the synthesis of zeolites EMC-1 (FAU) and EMC-2 (EMT) and conducted to the elaboration of new structure-directing agents and their bifunctional counterparts.MULHOUSE-SCD Sciences (682242102) / SudocSudocFranceF

A Reliable Method for the Preparation of Multiporous Alumina Monoliths by Ice-Templating

Alumina supports presenting a bimodal porosity are generally advantageous for the conversion of bulky molecules such as found in biomass, refining, and petrochemistry. However, shaping of such materials, while controlling pores size and orientation, proves to be hard. This problem can be tackled by using a simple method involving sol-gel chemistry, surfactant self-assembly, and ice-templating. Herein, a systematic study of the formulation and process parameters’ influence on the final material properties is presented. This protocol results in the repeatable preparation of centimeter-sized alumina monoliths presenting a uni-directional macroporosity and structured mesopores. These monoliths should be of particular interest in high flow rate catalytic applications

Freezing-induced ordering of block copolymer micelles

International audienceWe demonstrate here the ordering of block copolymer micelles by ice templating, below 0 degrees C. We used this for the preparation of silica monoliths that present an ice-templated macroporosity, combined with a 2D hexagonal mesostructure templated by the addition of P123. We propose a mechanism triggered by the progressive freezing-induced concentration

Hierarchical macroporous-mesoporous SBA-15 sulfonic acid catalysts for biodiesel synthesis

Hierarchical macroporous–mesoporous SBA-15 silicas have been synthesised via dual-templating routes employing liquid crystalline surfactants and polystyrene beads. These offer high surface areas and well-defined, interconnecting macro- and mesopore networks with respective narrow size distributions around 300 nm and 3–5 nm for polystyrene:tetraethoxysilane ratios ≥2:1. Subsequent functionalisation with propylsulfonic acid yields the first organized, macro-mesoporous solid acid catalyst. The enhanced mass transport properties of these new bi-modal solid acid architectures confer significant rate enhancements in the transesterification of bulky glyceryl trioctanoate, and esterification of long chain palmitic acid, over pure mesoporous analogues. This paves the way to the wider application of hierarchical catalysts in biofuel synthesis and biomass conversion

Formulation of metal-organic framework inks for the 3D printing of robust microporous solids

International audienceMetal-organic frameworks (MOFs) are a fast-growing class of highly porous materials owing to their exceptional structural diversity. A consequent effort has been deployed during the past few years for rationalizing the preparation of the most promising MOF structures, in view of their applications at larger scale. Still, their shaping represents a major bottleneck due to the difficulty to conciliate high porosity and adequate mechanical resistance to withstand overtime damaging stresses.3D printing is a promising technology as it allows the fast prototyping of materials at the macroscale.1 Herein, a 3D printer was modified to prepare a variety of MOF-based solids with controlled morphology from shear-thinning inks containing a cellulose-derived binder. Four benchmark MOFs were tested: HKUST-1, CPL-1, ZIF-8 and UiO-66-NH2. All solids are mechanically stable up to 0.6 MPa of uniaxial compression and highly porous, with BET specific surface areas lowered by 0 to -25%. Furthermore, these solids were applied to high pressure sorption (CH4, C2H4 and C2H6) and presented performances in line with the literature

Formulation of Metal–Organic Framework Inks for the 3D Printing of Robust Microporous Solids toward High-Pressure Gas Storage and Separation

International audienceThe shaping of metal−organic frameworks (MOFs) has become increasingly studied over the past few years, because it represents a major bottleneck toward their further applications at a larger scale. MOF-based macroscale solids should present performances similar to those of their powder counterparts, along with adequate mechanical resistance. Three-dimensional printing is a promising technology as it allows the fast prototyping of materials at the macroscale level; however, the large amounts of added binders have a detrimental effect on the porous properties of the solids. Herein, a 3D printer was modified to prepare a variety of MOF-based solids with controlled morphologies from shear-thinning inks containing 2-hydroxyethyl cellulose. Four benchmark MOFs were tested for this purpose: HKUST-1, CPL-1, ZIF-8, and UiO-66-NH 2. All solids are mechanically stable with up to 0.6 MPa of uniaxial compression and highly porous with BET specific surface areas lowered by 0 to −25%. Furthermore, these solids were applied to high-pressure hydrocarbon sorption (CH 4 , C 2 H 4 , and C 2 H 6), for which they presented a consequent methane gravimetric uptake (UiO-66-NH 2 , ZIF-8, and HKUST-1) and a highly preferential adsorption of ethylene over ethane (CPL-1)