Synthesis of chiral polymorph A-enriched zeolite Beta with an extremely concentrated fluoride route.
ABSTRACT: Chiral zeolitic materials with intrinsically chiral frameworks are highly desired because they can combine both shape selectivity and enantioselectivity. In the field of zeolite, the synthesis of chiral polymorph A of zeolite Beta or chiral polymorph A-enriched zeolite Beta is one of the biggest challenges. We demonstrate here a generalized extremely concentrated fluoride route for the synthesis of chiral polymorph A-enriched zeolite Beta in the presence of five achiral organic structure-directing agents. The polymorph A-enriched Ti-Beta shows a higher enantioselectivity for the asymmetric epoxidation of alkenes than the normal Ti-Beta.
Project description:The isomerization of 1,3-dihydroxyactone and d-glucose over Sn-Beta zeolite was investigated by in?situ 13 C?NMR spectroscopy. The conversion rate at room temperature is higher when the zeolite is dehydrated before exposure to the aqueous sugar solution. Mass transfer limitations in the zeolite micropores were excluded by comparing Sn-Beta samples with different crystal sizes. Periodic density functional theory (DFT) calculations show that sugar and water molecules compete for adsorption on the active framework Sn centers. Careful solvent selection may thus increase the rate of sugar isomerization. Consistent with this prediction, batch catalytic experiments show that the use of a co-solvent, such as tetrahydrofuran, that strongly interacts with the Sn centers suppresses glucose isomerization. On the other hand, the use of ethanol as cosolvent results in significantly higher isomerization activity in comparison with pure water because of decreased competition with glucose adsorption on zeolitic Sn sites.
Project description:Zeolite and zeolite-like molecular sieves are being used in a large number of applications such as adsorption and catalysis. Achievement of the long-standing goal of creating a chiral, polycrystalline molecular sieve with bulk enantioenrichment would enable these materials to perform enantioselective functions. Here, we report the synthesis of enantiomerically enriched samples of a molecular sieve. Enantiopure organic structure directing agents are designed with the assistance of computational methods and used to synthesize enantioenriched, polycrystalline molecular sieve samples of either enantiomer. Computational results correctly predicted which enantiomer is obtained, and enantiomeric enrichment is proven by high-resolution transmission electron microscopy. The enantioenriched and racemic samples of the molecular sieves are tested as adsorbents and heterogeneous catalysts. The enantioenriched molecular sieves show enantioselectivity for the ring opening reaction of epoxides and enantioselective adsorption of 2-butanol (the R enantiomer of the molecular sieve shows opposite and approximately equal enantioselectivity compared with the S enantiomer of the molecular sieve, whereas the racemic sample of the molecular sieve shows no enantioselectivity).
Project description:The liquid-phase epoxidation of cyclopentene (CPE) was performed in the Ti-zeolite/H2O2 catalytic system for the clean synthesis of cyclopentene oxide. Among all the Ti-zeolites (Ti-Beta, Ti-MOR, Ti-MCM-68, TS-1, TS-2, and Ti-MWW) investigated in the present study, Ti-MWW provided relatively lower CPE conversion of 13% due to the diffusion constrains but a higher CPO selectivity of 99.5%. The catalytic performance of Ti-MWW was significantly enhanced by piperidine (PI) treatment, with the CPE conversion and CPO selectivity increased to 97.8 and 99.9%, respectively. The structural rearrangement upon PI treatment converted the 3-dimensional (3D) MWW structure to a 2D lamellar one, which enlarged the interlayer space and greatly alleviated the diffusion constrains of cyclic cyclopentene. Furthermore, the newly constructed "open site" six-coordinated Ti active sites with PI as the ligand exhibited higher catalytic activity. The two factors contributed to more significant enhancement of the activity upon PI-assisted structural arrangement compared to the cases in linear alkenes.
Project description:An innovative and facile synthesis of cobalt based inorganic pigment was carried out by means of a low energy thermal conversion of a cobalt-exchanged zeolite. The Na-A [LTA] zeolite was used, since it is a low cost and easily available raw material. The ion exchange mechanism allowed to control, at microscopic level, the composition of the zeolitic precursor. Several chromatic effects could be obtained by varying the treatment temperature and/or the cobalt concentration in the contact solution. The reliability of these new zeolite-based pigments was tested in porcelain manufacture, in collaboration with the Institute for the Capodimonte porcelain "Giovanni Caselli". The developed cobalt pigments were successfully tested either in the porcelain mixture to obtain a coloured product or in the decoration step (such as ingobbio, colored glazes and "third fire decoration").
Project description:The chemistry between layered MWW zeolite and carbon black pearls (BP 2000) as an inexpensive hard template was investigated to develop a rational one-pot synthesis of MCM-22 microspheres. The characterization results showed that the insertion of BP 2000 in the gel synthesis did not substantially compromise the crystallinity and microporosity, and the microscopic analyses showed that BP 2000 played a key role in controlling the final morphology of the MCM-22 zeolite, creating beautiful dandelion-like microspherical particles. The morphology obtained is due to the tortuous shape of the hard template, the particular MWW particle crystals, the interaction with the external surface of the MWW zeolitic precursor, and the synthesis conditions. The stacking of MWW crystals with edge-to-face orientations generates meso-/macrovoids, allowing access to the interiors of the microspheres. The microspheres were homogeneous with sizes ranging from 6 to 8 ?m with an increase of the external surface and a macroporous size distribution centered at 200 nm, which is two times that of the traditional MCM-22 zeolite.
Project description:A hydrothermal rota-crystallization method is developed for the one-step synthesis of a hollownest-structured zeolite precursor with the shell composed of autogenously-intergrown MWW nanosheet crystals containing a large number of stacking-pores without using any porogen or hard scaffold. This material possesses a large external surface area. By simple acid washing, the resultant Ti-containing catalyst can be directly used in the epoxidation of alkenes with hydrogen peroxide. The excellent catalytic activity over the Ti-HSZ catalyst is assumed to be due to the exposure of more Ti active sites over the MWW nanosheet crystals in the shell of the catalyst. More importantly, this Ti-HSZ catalyst washed with H2O2/ethanol solution has been reused 6 times without an appreciable decrease in both the conversion of the allyl chloride and the selectivity of the epichlorohydrin, which is ascribed to the structural stability of the hollownest-structured zeolite.
Project description:The herein reported work describes the development of hierarchically-organized fluorescent nanomaterials inspired by plant antenna systems. These hybrid materials are based on nanostructured zeolitic materials (LTL zeolite) doped with laser dyes, which implies a synergism between organic and inorganic moieties. The non-interconnected channeled structure and pore dimensions (7.1 Å) of the inorganic host are ideal to order and align the allocated fluorophores inside, inferring also high thermal and chemical stability. These artificial antennae harvest a broad range of chromatic radiation and convert it into predominant red-edge or alternatively white-light emission, just choosing the right dye combination and concentration ratio to modulate the efficiency of the ongoing energy transfer hops. A further degree of organization can be achieved by functionalizing the channel entrances of LTL zeolite with specific tailor-made (stopcock) molecules via a covalent linkage. These molecules plug the channels to avoid the leakage of the guest molecules absorbed inside, as well as connect the inner space of the zeolite with the outside thanks to energy transfer processes, making the coupling of the material with external devices easier.
Project description:Perfluoroalkylglucosides comprise a very important class of fluorine-containing surfactants. These compounds can be synthesized by using the Fisher reaction, starting directly from glucose and the required perfluoroalcohols. We wish to report on the use of zeolite catalysts of different structure and composition for the synthesis of perfluoroalkylglucosides when using glucose and 1-octafluoropentanol as substrates. Zeolites of different pore architecture have been chosen (ZSM-5, ZSM-12, MCM-22 and Beta). Zeolites were characterized by XRD, nitrogen sorption, scanning electron microscopy (SEM) and solid-state 27Al MAS NMR spectroscopy. The activity of the zeolite catalysts in the glycosidation reaction was studied in a batch reactor at 100 °C below atmospheric pressure. The performance of zeolites was compared to other catalysts, an ion-exchange resin (Purolite) and a montmorillonite-type layered aluminosilicate. The catalytic performance of zeolite Beta was the highest among the zeolites studied and the results were comparable to those obtained over Purolite and montmorillonite type catalysts.
Project description:The tremendous potential of zeolite membranes for efficient molecular separation via size-exclusion effects is highly desired by the energy and chemical industries, but its practical realization has been hindered by nonselective permeation through intercrystalline spaces and high resistance to intracrystalline diffusion in the conventional zeolite membranes of randomly oriented polycrystalline structures. Here, we report the synthesis of ZSM-5 zeolite nanosheets with very large aspect ratios and nanometer-scale thickness in the preferred straight channel direction. We used these ZSM-5 nanosheets to fabricate ultrathin (<500 nm) laminated membranes on macroporous alumina substrates by a simple dip-coating process and subsequent consolidation via vapor-phase crystallization. This ultrathin b-oriented ZSM-5 membrane has demonstrated extraordinary water flux combined with high salt rejection in pervaporation desalination for brines containing up to 24 weight % of dissolved NaCl. The ZSM-5 nanosheets may also offer opportunities to developing high-performance battery ion separators, catalysts, adsorbents, and thin-film sensors.
Project description:Mesostructured zeolitic materials (MZMs) with relatively high acidity in comparison with the mesoporous siliceous MCM-41 were prepared via an efficient, mild, and simple post-synthetic treatment of Y zeolite facilitated by microwave irradiation, i.e., microwave-assisted chelation (MWAC). The disordered mesoporous aluminosilicates materials (DMASs) of MZM were created from Y zeolite in the absence of using mesoscale templates. The prepared DMASs showed the good mesoporous features with the mesopore area and volume of ~260 m2 g-1 and ~0.37 cm3 g-1, respectively, and with the mesopore sizes distributed in a range of 2-10 nm. MZMs possess a total acidity of about 0.6 mmol g-1 and exhibited comparatively superior catalytic activity to the parent Y zeolite and MCM-41 in the vapor phase catalytic dealkylation of 1,3,5-triisopropylbenzene (TiPBz) and liquid phase catalytic aldol condensation of benzaldehyde with 1-heptanal. Although the yield loss was inevitable for preparing MZMs using the MWAC method, the preliminary economic analysis of the preparation cost of MZMs showed the promise. Additionally, a comprehensive comparison of the state-of-the-art mesoporous materials concerning their sustainable aspects was made, showing that MZMs are promising mesoporous materials for further development and functionalization for catalysis.