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zeolites with AST-topology causes reduction of the framework, hence structural destruction, in a notable extension. This is due to the impossibility for the organic cation occluded inside to react with ambient oxygen. As the temperature increases, reoxidation in air of the reduced framework causes episodes of weight-gain. When calcination is carried out in N2, weight losses close to 70% imply a loss of Ge due to sublimation of germanium monoxide, GeO. The nature of the organic cation occluded determines the nature and oxidation state of the final residue after calcination in N2: for tetramethylammonium the residue is GeO2 while trimethyl-terc-butylammonium, thanks to its larger C content, yields metallic Ge. Framework organoreduction is not unique to GeO2-AST zeolites but also occurs during the calcination in air of other germanium-containing zeolites with larger pore openings. [ABSTRACT FROM AUTHOR]

A synthesis of zeolite-like aluminogermanates using N,N,N-trimethyl-terc-butylammonium (TMTBA) and fluoride evolved from an initially crystallized zeolite with the AST Zeolite Framework Type and very little Al in it into an Al-free GeO2 phase with the same structure but a slightly smaller unit cell. In spite of both zeolites having the same framework type, same symmetry, a much similar unit cell size and almost the same framework composition, phase segregation occurred at intermediate crystallization times as the initial AST phase was gradually replaced by the new one. For reaction mixtures with a high Al content complete replacement of the large cell by the smaller cell phase was accomplished. The solids have been characterized by powder X-ray diffraction (XRD), Rietveld refinement from synchrotron diffraction data, multinuclear Nuclear Magnetic Resonance (NMR) of both intact and disolved solids and infrarred spectroscopy. The study reveals TMTBA can degrade under the crystallization conditions to initially yield triethylamine (tMA), whereas transmethylation between TMTBA and tMA produces tetramethylammonium (TMA), as probed by liquid NMR. The TMA cation can also structure-direct to AST zeolites but with a smaller unit cell volume and no Al in the framework. Phase segregation occurs despite the lack of structural mismatch because both crystallization events are decoupled, occurring at different moments and from largely different solutions. When both TMTBA and TMA cations are intentionally added at the start, no phase segregation but crystallization of a solid solution occurs instead. [ABSTRACT FROM AUTHOR]

2-Ethyl-1,3,4-trimethylimidazolium is so far the fifth and largest imidazolium cation able to produce the pure silica zeolite ITW. The crystallization is not direct, but occurs as an in situ transformation from either the chiral HPM-1 (STW) zeolite or the new layered zeolite precursor HPM-2 (preMTF) and results in large interpenetrated crystals with a habit so far unseen in this zeolite. The results of chemical, physicochemical and structural characterization allow us to discuss structure-direction issues. The large cation is occluded intact in the zeolite, causing an expansion of the zeolite volume. The degree of polarization of the Si-O bond is similar to that observed in other as-made ITW zeolites. [ABSTRACT FROM AUTHOR]

HPM-2 is a new organosilicate layeredmaterial synthesized by thefluoride route using 2-ethyl-1,3,4-trimethylimidazolium. The layersare of a new structural type (denoted mtf) and are held together bystrong hydrogen bonds giving rise to a 1H magic angle spinning(MAS) nuclear magnetic resonance (NMR) at around 16 ppm and by Coulombicinteractions between silanolates and the organic cations residingin the interlayer space. Upon calcination HPM-2 transforms into thepure silica MTF zeolite by topotactic condensation, a process thatis essentially completed at 400 °C. Attempts to apply known methodsto derive new materials (swelling, delamination, interlayer expansion)are described. In the case of the interlayer expansion reaction, anonmicroporous dense phase is obtained, which is likely due to anunfavorable disposition of silanols in close couples within each layer.Silanol condensation between the newly incorporated silicon speciesoccurs across the main window producing narrower (6 member ring, 6MR)rather than wider (10MR) windows. [ABSTRACT FROM AUTHOR]

The light hydrocarbon sorption properties of the three 8-ring zeolites, pure silica Si-CHA and ITQ-3 and high silica ZSM-58 (DDR structure type), have been measured and the adsorption rates and adsorption energies of ethene, ethane, propane and propene were determined. Of particular interest is the large difference in the rates of adsorption of propene and propane exhibited by each of these zeolites. For Si-CHA the ratio of the D’s is 43,000 at 30 °C and the activation energies for diffusion of propene and propane are ∼10 and 73 kJ/mol, respectively, indicating that activated diffusion controls the diffusion rate of propane through its 8-rings. The diffusivity decreases in the order ethene ∼ ethane > propene ≫ propane > n-hexane. All three zeolites have potential for the separation of propene from propene/propane mixtures. [Copyright &y& Elsevier]

An organic cation lacking specificity in its structure-directing action offers the possibility, through the screening of other structure-directing parameters, to synthesize a variety of zeolites. In this work we show that the organic structure-directing agent 2-isopropyl-1,3-dimethylimidazolium (2iPr13DMI) can produce up to seven different zeolite phases depending on water concentration, the presence of inorganic impurities, crystallization temperature and time, and germanium molar fraction. The obtained phases are very different in terms of pore system, connectivity of the zeolite structure and structural units. At the pure SiO2 side, ZSM-12 and SSZ-35 dominate, with ZSM-12 being favored by the presence of potassium impurities and by less concentrated conditions. The introduction of Ge at low levels favors SSZ-35 over ZSM-12 and as the Ge fraction increases it successively affords CSV, -CLO and two distinct UOS zeolites, HPM-11 and HPM-6. These two zeolites have the same topology but distinct chemical compositions and display powder X-ray diffraction patterns that are much different from each other and from that of as-synthesized IM-16 (UOS reference material). They also show different symmetry at 96 K. Rietveld refinements of the three as-made UOS materials mentioned are provided. HPM-6 and HPM-11 are produced in distinct, non-adjacent crystallization fields. The frequent cocrystallization of the chiral STW zeolite, however, did not afford its synthesis as a pure phase. Molecular mechanics simulations of the location of the organic cation and host–guest interactions fail to explain the observed trends, but also considering the intrinsic stability of the zeolites and the effect of germanium help to rationalize the results. The study is completed by DFT calculations of the NMR chemical shifts of 13C in UOS (helping to understand splittings in the spectrum) and 19F in CSV (supporting the location of fluoride inside the new [4452], which is an incomplete double 4-ring). [ABSTRACT FROM AUTHOR]

As the spacer length in 1,2‐dimethylimidazolium‐based dications increases beyond a specific point (six methylene units), they fail in structure‐directing towards STW zeolites in any synthetic conditions. These dications can instead produce, under fluoride concentrated conditions, either *BEA [in the case of the eight‐methylene‐unit structure‐directing agent (SDA)] or MWW (ten methylene units) zeolites. For any length of the dication, the default zeolite (MTW) is a relatively dense zeolite containing a unidimensional channel, whereas the zeolite demanding most specificity (STW, *BEA or MWW) is more porous, affording a larger concentration of the dication to be occluded. This work provides the first reported fluoride synthesis of pure silica MWW zeolites. Charge balance of the organic dications in this zeolite was achieved by combining "structural" silanolates, regular "connectivity defects" and occluded fluoride. Molecular mechanics calculations showed a perfect fit of the decamethylenebis(dimethylimidazolium) dication in the sinusoidal intralayer pore system of MWW. The calculations showed also that the dication is able to stabilize the interlayer space without disturbing the hydrogen‐bonding system that holds the layers together in the as‐made material. The 19F magic‐angle spinning (MAS) NMR presented two distinct resonances at −71 and −83 ppm, which, on the basis of DFT calculations, we tentatively assigned to fluoride occluded in [4662] and [415262] cages of the MWW structure, respectively. The same DFT study determines a different chemical shift of one methyl 13C nuclear magnetic resonance according to the imidazolium ring residing in the sinusoidal channels or in the large cup cavities, thus explaining an experimentally observed splitting of that resonance. Pure silica MWW zeolite was synthesized for the first time through the fluoride route by using dimethylimidazolium‐based long dications in highly concentrated conditions. DFT calculations suggested that the F− anions reside in both [415262] and [4662] cages, giving rise to two distinct 19F NMR signals. [ABSTRACT FROM AUTHOR]

Length-dependent structure direction of linear methylimidazolium-based dications towards MFI zeolite, previously known only for the tetramethylene spacer, has also been found for octamethylene and decamethylene spacers. This works only under highly concentrated conditions, whereas dilution always tends to favor TON, a default structure that is the only zeolite obtained with the other reported dications (with tri-, penta-, and hexamethylene spacers). The locations and conformations of the dications have been studied by molecular mechanics simulations. As longer dications introduce lower density of positive charges in the zeolite, the density of connectivity defects also decreases. Finally, these long dications cannot easily place each charged imidazolium ring in the two possible orientations (either parallel or perpendicular to 4MR close to F− sites) found for the tetramethylene case. Hence, although the three MFI materials display two 19F NMR resonances at similar chemical shifts, their relative intensities strongly vary as a function of the spacer length. [ABSTRACT FROM AUTHOR]

Abstract: Molecular simulation, through the computation of adsorption isotherms, is a useful predictive tool for the selective capacity of nanoporous materials. Generally, adsorbents are modelled as rigid frameworks, as opposed to allowing for vibrations of the lattice, and this approximation is assumed to have negligible impact on adsorption. In this work, this approach was tested in an especially challenging system by computing the adsorption of the chiral molecules 2‐pentanol, 2‐methylbutanol and 3‐methyl‐2‐butanol in the all‐silica and germanosilicate chiral zeolites STW and studying their lattice vibrations upon adsorption. The analysis of single‐ and multicomponent adsorption isotherms showed the suitability of STW‐type zeolites as molecular sieves for chiral separation processes, which pose a challenging task in the chemical and pharmaceutical industries. Moreover, new experimental adsorption data validate the force field employed. The results reveal that the lattice vibrations of the all‐silica framework are sorbate‐independent, while those of germanosilicate STW show host–guest coupling modulated by uptake and sorbate type that disrupts the chiral recognition sites. This study indicates that the effects of intrinsic flexibility on the selective capacity of nanoporous materials may range from low to high impact, and some of them could not have been foreseen even after examination of the structural dynamics of an empty framework. [ABSTRACT FROM AUTHOR]

Zeolites are microporous silicates with a large variety of applications as catalysts, adsorbents, and cation exchangers. Stable silica-based zeolites with increased porosity are in demand to allow adsorption and processing of large molecules but challenge our synthetic ability. We report a new, highly stable pure silica zeolite called ZEO-3, which has a multidimensional, interconnected system of extra-large pores open through windows made by 16 and 14 silicate tetrahedra, the least dense polymorph of silica known so far. This zeolite was formed by an unprecedented one-dimensional to three-dimensional (1D-to-3D) topotactic condensation of a chain silicate. With a specific surface area of more than 1000 square meters per gram, ZEO-3 showed a high performance for volatile organic compound abatement and recovery compared with other zeolites and metal-organic frameworks. [ABSTRACT FROM AUTHOR]

The transformation from a disordered into an ordered version of the zeolite natrolite occurs on prolonged heating of this material in the crystallizing medium, but not if the mother liquor is replaced by water or an alkaline solution. This process occurs for both aluminosilicate and gallosilicate analogues of natrolite. In cross experiments, the disordered Al-containing (or Ga-containing) analogue is heated while in contact with the mother liquor of the opposite analogue, that is, the Ga-containing (or Al-containing) liquor. Therefore, strong evidence for the mechanism of the ordering process was obtained, which was thus proposed to proceed by intraframework migration of tetrahedral atoms without diffusion along the pores. Migration is first triggered, then fuelled by surface rearrangement through reactions with the mother liquor, and stops when an almost fully ordered state is attained. Classical dissolution-recrystallization and Ostwald ripening processes do not appear to be relevant for this phase transformation. [ABSTRACT FROM AUTHOR]

The transformation from a disordered into an ordered version of the zeolite natrolite occurs on prolonged heating of this material in the crystallizing medium, but not if the mother liquor is replaced by water or an alkaline solution. This process occurs for both aluminosilicate and gallosilicate analogues of natrolite. In cross experiments, the disordered Al-containing (or Ga-containing) analogue is heated while in contact with the mother liquor of the opposite analogue, that is, the Ga-containing (or Al-containing) liquor. Therefore, strong evidence for the mechanism of the ordering process was obtained, which was thus proposed to proceed by intraframework migration of tetrahedral atoms without diffusion along the pores. Migration is first triggered, then fuelled by surface rearrangement through reactions with the mother liquor, and stops when an almost fully ordered state is attained. Classical dissolution-recrystallization and Ostwald ripening processes do not appear to be relevant for this phase transformation. [ABSTRACT FROM AUTHOR]

Zeolites are crystalline porous materials with important industrial applications, including uses in catalytic and adsorption-separation processes. Access into and out of their inner confined space, where adsorption and reactions occur, is limited by their pore apertures. Stable multidimensional zeolites with larger pores able to process larger molecules are in demand in the fine chemical industry and for the oil processing on which the world still relies for fuels. Currently known extra-large-pore zeolites display poor stability and/or lack pore multidimensionality, limiting their usefulness. We report ZEO-1, a robust, fully connected aluminosilicate zeolite with mutually intersecting three-dimensional extra-large plus three-dimensional large pores. ZEO-1 is stable up to 1000°C, has an extraordinary specific surface area (1000 square meters per gram), and shows potential as a catalytic cracking catalyst. [ABSTRACT FROM AUTHOR]

One common strategy in the search for new zeolites is the use of organic structure‐directing agents (OSDA). Typically, one seeks to achieve a high specificity in the structure‐directing effect of the OSDA. This study shows, however, that an OSDA lacking strong specificity towards any particular zeolite may provide opportunities for discovery when other synthesis parameters are systematically screened. Thus, 1‐methyl‐2‐ethyl‐3‐n‐propylimidazolium has allowed to crystallize the new large/medium pore zeolite HPM‐16 as well as the recently reported extra‐large pore ‐SYT and the medium/small pore and chiral STW. The sophisticated OSDA originally affording ‐SYT and the new simple OSDA have very little in common, both in terms of size, shape and flexibility, while both may still direct the synthesis of the same zeolite. In fact, molecular simulations show that the new OSDA is located in three different positions of the ‐SYT structure, including the discrete 8MR where the original organic could not fit. [ABSTRACT FROM AUTHOR]

A series of doubly charged structure-directing agents based on two methylimidazolium moieties linked by a linear bridge of n = 3,4,5, or 6 methylene groups has been used in the synthesis of pure silica zeolites in the presence of fluoride. All of them yielded zeolite TON while only the one with n = 4 was able to produce also zeolite MFI at highly concentrated conditions. In this MFI zeolite, two distinct 19F MAS NMR resonances with about equal intensity were observed, indicating two different chemical environments for occluded fluoride. With the singly charged 1-ethyl-3-methylimidazolium cation, which can be formally considered as the "monomer" of the bis-imidazolium cation with n = 4, TON and MFI were also obtained, and again two 19F MAS NMR resonances now with largely dissimilar intensities were observed in MFI. Molecular mechanics simulations support a commensurate structure-direction effect for n = 4 in MFI, with each imidazolium ring, in two different orientations, sitting close to the [415262] cage. Periodic DFT calculations suggest that F in MFI resides always in the [415262] cages, with the different 19F resonances observed being due to the different orientation of the closest imidazolium ring. [ABSTRACT FROM AUTHOR]

Three gallosilicate natrolites with closely similar chemical composition but differing in the distribution of Si and Ga over crystallographically different tetrahedral sites (T-sites) show striking differences in their cation exchange performance. The ability to exchange Na+ by the larger alkali metal cations decreases upon increasing the size of the cation, as expected, but also with the degree of T-atom ordering. To seek an insight into this phenomenon, the crystal structures of 11 different zeolites, which show variations in degree of T-atom ordering, nature of countercation, and hydration state, have been refined using synchrotron diffraction data. While the three as-made sodium materials were characterized to have a low, medium, and high degree of ordering, respectively, their pore sizes are close to the size of the bare Na+ cation and much smaller than that of the larger alkali cations, which are nonetheless exchanged into the materials, each one at a different level. Interestingly, large differences are also manifested when the Na+ back-exchange is performed on the dehydrated K+ forms, with crystallographic pore sizes too small even to allow the passage of Na+. Although the thermodynamic data point to small differences in the enthalpy of the Na+/K+ exchange in the three materials, comparison of the "static" crystallographic pore sizes and the diameter of the exchanged cations lead us to conclude that during the exchange process these zeolites undergo significant deformations that dynamically open the pores, allowing cation traffic even for Cs+ in the case of the most disordered material. In addition to the very large topological flexibility typical of the natrolite framework, we propose as a hypothesis that there is an additional flexibility mechanism that decreases the rigidity of the natrolite chain itself and is dependent on preferential siting of Si or Ga on crystallographically different T-sites. [ABSTRACT FROM AUTHOR]

As-made and calcined ITQ-12 zeolites are structurally characterized by means of the analysis of their vibrational modes. The experimental IR spectra made on high crystalline samples are compared with accurate B3LYP periodic calculations performed with the CRYSTAL06 code. The fair agreement between both sets of data allows us to make a reliable assignment of the IR modes. Thanks to the detailed information provided by the theoretical calculations, the analysis of the IR intensities, the Born dynamic charges, and the whole set of vibrational frequencies at Γ-point shed light on several aspects of the host-guest interaction, structure-direction issues, including the role of fluoride anions in allowing the crystallization of silica structures with strained double-four rings, and the role played by the framework flexibility. [ABSTRACT FROM AUTHOR]

HPM‐16 is a highly porous germanosilicate zeolite with an interrupted framework that contains a three‐dimensional system of 12+10×10(12)×12+10‐membered ring (MR) pores. The 10(12) MR pore in the b direction is a 10 MR pore with long 12 MR stretches forming 30 Å long tubular supercages. Along one direction the 10 MR pores are fused, meaning that the separation between adjacent pores consists of a single tetrahedron that is, additionally, connected to only three additional tetrahedra (a Q3). These fused pores are thus decorated by T‐OH groups along the whole diffusion path, creating a hydrophilic region embedded in an otherwise essentially hydrophobic environment. The structure is built from highly porous 12×12×12 MR uninterrupted layers that are connected to each other through Q3 producing a second system of 10×10×10 MR pores. This zeolite can be extensively degermanated yielding a material with high thermal stability, despite its interrupted nature. [ABSTRACT FROM AUTHOR]

HPM‐16 is a highly porous germanosilicate zeolite with an interrupted framework that contains a three‐dimensional system of 12+10×10(12)×12+10‐membered ring (MR) pores. The 10(12) MR pore in the b direction is a 10 MR pore with long 12 MR stretches forming 30 Å long tubular supercages. Along one direction the 10 MR pores are fused, meaning that the separation between adjacent pores consists of a single tetrahedron that is, additionally, connected to only three additional tetrahedra (a Q3). These fused pores are thus decorated by T‐OH groups along the whole diffusion path, creating a hydrophilic region embedded in an otherwise essentially hydrophobic environment. The structure is built from highly porous 12×12×12 MR uninterrupted layers that are connected to each other through Q3 producing a second system of 10×10×10 MR pores. This zeolite can be extensively degermanated yielding a material with high thermal stability, despite its interrupted nature. [ABSTRACT FROM AUTHOR]

HPM‐14 is a new extra‐large pore zeolite synthesized using imidazolium‐based organic structure‐directing agents (SDAs), fluoride anions, and germanium and silicon as tetrahedral components of the framework. Owing to the presence of stacking disorder, the structure elucidation of HPM‐14 was challenging, and different techniques were necessary to clarify the details of the structure and to understand the nature of the disorder. The structure has been solved by three‐dimensional electron‐diffraction technique (3D ED) and consists of an intergrowth of two polymorphs possessing a three‐dimensional channel system, including an extra‐large pore opened through windows made up of sixteen tetrahedral atoms (16‐membered ring, 16MR) as well as two additional sets of odd‐membered (9MR) and small (8MR) pores. The intergrowth has been studied by scanning transmission electron microscopy (Cs‐STEM) and powder X‐ray diffraction simulations (DIFFaX), which show a large predominance of the monoclinic polymorph A. [ABSTRACT FROM AUTHOR]

HPM‐14 is a new extra‐large pore zeolite synthesized using imidazolium‐based organic structure‐directing agents (SDAs), fluoride anions, and germanium and silicon as tetrahedral components of the framework. Owing to the presence of stacking disorder, the structure elucidation of HPM‐14 was challenging, and different techniques were necessary to clarify the details of the structure and to understand the nature of the disorder. The structure has been solved by three‐dimensional electron‐diffraction technique (3D ED) and consists of an intergrowth of two polymorphs possessing a three‐dimensional channel system, including an extra‐large pore opened through windows made up of sixteen tetrahedral atoms (16‐membered ring, 16MR) as well as two additional sets of odd‐membered (9MR) and small (8MR) pores. The intergrowth has been studied by scanning transmission electron microscopy (Cs‐STEM) and powder X‐ray diffraction simulations (DIFFaX), which show a large predominance of the monoclinic polymorph A. [ABSTRACT FROM AUTHOR]

The new zeolite NUD-3 possesses a three-dimensional system of large pore channels that is topologically identical to those of ITQ-21 and PKU-14. However, the three zeolites have distinctly different frameworks: a particular single 4-membered ring inside the denser portion of the zeolite is missing in PKU-14, disordered in ITQ-21 and fully ordered in NUD-3. We document these differences and use molecular simulations to unravel the mechanism by which a particular structure directing agent dication, 1,1′-(1,2-phenylenebis(methylene))bis(3-methylimidazolium), is able to orient this inner ring. [ABSTRACT FROM AUTHOR]

IDM‐1 is a new silica zeolite with an ordered and well‐defined framework constructed by alternating pentasil layers and interrupted layers, giving rise to an intersecting system of straight medium pores and undulating extra‐large lobed pores. This unique structure was solved by rotation electron diffraction and refined against synchrotron powder X‐ray diffraction data. Despite the presence of both Si(OSi)3(OH) and Si(OSi)2(OH)2 sites, this new zeolite presents high thermal stability, withstanding calcination even to 1000 °C. The location of defects at specific sites of the structure results in alternating hydrophobic SiO2 and hydrophilic SiO(2−x)(OH)2x intracrystalline regions. This peculiar combination of intersecting medium and extra‐large pores and alternating regions of different chemical character may provide this zeolite with unique catalytic properties. [ABSTRACT FROM AUTHOR]

IDM‐1 is a new silica zeolite with an ordered and well‐defined framework constructed by alternating pentasil layers and interrupted layers, giving rise to an intersecting system of straight medium pores and undulating extra‐large lobed pores. This unique structure was solved by rotation electron diffraction and refined against synchrotron powder X‐ray diffraction data. Despite the presence of both Si(OSi)3(OH) and Si(OSi)2(OH)2 sites, this new zeolite presents high thermal stability, withstanding calcination even to 1000 °C. The location of defects at specific sites of the structure results in alternating hydrophobic SiO2 and hydrophilic SiO(2−x)(OH)2x intracrystalline regions. This peculiar combination of intersecting medium and extra‐large pores and alternating regions of different chemical character may provide this zeolite with unique catalytic properties. [ABSTRACT FROM AUTHOR]

A short imidazolium based dication, with only three methylene units in the spacer linker, selectively directs the crystallization of zeolite HPM-12 (*UOE) as long as there is enough germanium present in the synthesis gel. The integrity of the dication is proved by dissolution of the zeolite and 1H and 13C NMR spectroscopy, where significant effects of organic dication concentration and the presence and concentration of HF need to be taken into account. For the as-made HPM-12 zeolite, a large shift of 9 ppm of one resonance in the 13C MAS NMR spectrum is due to the particular conformation of the dication imposed by confinement in the zeolite framework, as found by DFT calculations. The structure-directing ability of this kind of dication with varying length of the linker suggests that matching of the distance between positive charges (imidazolium moieties) and negative charges (double four rings in which fluoride resides) plays a crucial role during crystallization. [ABSTRACT FROM AUTHOR]

Gas adsorption over zeolites is at the basis of important applications of this class of microporous crystalline solids, notably as separation media and catalysts, but it may also be complex and not straightforward to understand. Here we report that for temperature below 323 K propane adsorption on the small-pore pure-silica zeolite ITW exhibits a clear step (pseudosaturation). This is absent in the case of propene and the other small linear alkanes. An intermediate plateau, clearly observed in the 293 K isotherm, always occurs when one molecule of propane is loaded in every other cage, i.e., at half-saturation. The simulation results show a swelling of the ITW structure upon propane adsorption. The strong dependence of available pore volume on the adsorbate loading level implies that adsorption cannot occur on the void structure while saturation can only be reached on highly loaded structures. To account for this unprecedented adsorption phenomenon, we propose the term "guest-modulated effect". [ABSTRACT FROM AUTHOR]

HPM-5, a porous aluminosilicate with an intricate and so far unsolved structure, has been synthesized by using 1,2,3-trimethylimidazolium in hydroxide medium in the absence of fluoride anions. It consistently displays an ill-defined XRD pattern with broad and overlapped reflections and contains a large concentration of defects, as evidenced by IR and 29Si MAS NMR spectroscopy. 1H MAS NMR spectroscopy confirmed the existence of highly deshielded protons (δ = -11.6 ppm) assigned to hydrogen atoms in relatively strong Si-O-H. . . .O-Si hydrogen bonds (O···O distance ≈ 2.64 Å) The calcined material shows limited microporosity (0.07-0.09 cm3

Focuses on the synthesis of the stable inorganic electrides. Optical and magnetic properties of electrides; Addition of alkali metals to alumino-silicate zeolites; Interactions of neutral cesium atom with the silica lattice.

2-Ethyl-1,3,4-trimethylimidazolium is a poor organic structure-directing agent in the synthesis of pure silica zeolites using fluoride as a mineralizer at 150 °C. Under these conditions only ill-crystallized solids are obtained after long hydrothermal treatments (several weeks). It disappoints despite its relatively large size, conformational rigidity, and intermediate hydrophilic/hydrophobic character, attributes which would qualify it as a promising structure-directing agent, according to prior investigations. By raising the crystallization temperature to 175 °C under otherwise identical conditions, crystallization is dramatically accelerated. Depending on the water/silica ratio and crystallization time, two different materials are obtained: the recently reported pure silica polymorph of the chiral STW-type zeolite, HPM-1, and the new layered organosilicate, HPM-2. Prolonged heating transforms these phases into the small-pore ITW-type zeolite, while no signs of the SOF-type zeolite (formally built from the same layers as STW) was found. A complete physicochemical and structural characterization of the as-made chiral HPM-1 zeolite is provided, and the proposed stabilization of this zeolite by polarization of the Si–O bond is supported by the observed deviation from tetrahedrality. HPM-1 is optically active, and a study of several crystallites by Mueller matrix microscopy shows that their optical activity can be individually measured and that this technique could be useful for the assessment of the enantiomeric purity of a microcrystalline powder. [ABSTRACT FROM AUTHOR]

Pure silica ITW zeolite can be synthesized using 1,2,3-trimethylimidazolium and 1,3-dimethylimidazolium cations and fluoride anions as structure-directing agents (SDAs). Similarly to the previously reported 1,3,4-trimethylimidazolium, the dimethyl cation can also produce the zeolite TON, but this higher framework density phase finally transforms in situ into ITW. The structures of the as-made and calcined phases prepared with the new cations show a unit cell doubling along z, and the refined structures are reported. Periodic Density Functional Theory calculations provide the energies of the six SDA-ITW and SDA-TON zeolites, and their relative stabilities fully agree with the experimental observations. Structure-direction in this system is discussed from experimental and theoretical results that give strong support to the idea that strained silica frameworks are made possible in fluoride media by decreasing the covalent character of the Si-O bond. This decreased covalency is enhanced with the 1,2,3-trimethyl isomer, which is shown to be the strongest SDA for ITW and, at the same time, is the more hydrophilic of the three SDAs tested. Our observations with the three SDAs agree with the so-called Villaescusa's rule, i.e., the low framework density phase is favored at higher concentrations, but at the same time question the supersaturation hypothesis that has been proposed to explain this rule, since here the low-density phase is the most stable one. [ABSTRACT FROM AUTHOR]

Under specific synthesis conditions the crystallization of a dense silica zeolite (TON) is followed by its in situ transformation into a less dense and, in the absence of occluded species, less stable zeolite (ITW). Periodic ab initio calculations including energy corrections for van der Waals interactions as well as zero-point and thermal effects are used first to assess the relative stability of both SiO2 (calcined) phases and then to investigate host-guest interactions in the as-made zeolites, as well as their relative stability. The less dense SiO2-ITW is less stable than SiO2-TON, with an energy difference that is significantly larger than expected from their difference in molar volume. This extra destabilization is ascribed to the strained double 4-ring units of silica tetrahedra (D4R). Regarding the as-made materials, the organic cation fills in more efficiently the zeolitic voids in ITW than in TON, bringing about a larger stabilization in the former owing to the extension of the long-range addition of dispersion force contributions. On the other hand, fluoride induces a polarization of the silica framework that is highly localized in TON (showing pentacoordinated [SiO4/2F]- units) but has a large global character in ITW (where fluoride is encapsulated into D4R units). We argue that the structure-directing role toward D4R materials that has been proposed for fluoride consists fundamentally in the ability to induce a global polarization of the silica framework that allows relaxation of the strain associated with these units. In this sense, fluoride stabilizes the otherwise strained D4R-SiO2 frameworks making them reachable for crystallization. This work documents a case in which the structure directing agents "choose" a structure not kinetically but through stabilization. [ABSTRACT FROM AUTHOR]

Silicone and pure organic binders were used to develop FAU-type zeolite coatings applied on pre-treated aluminum substrates by using a spraying method and then cured under specific conditions. The influence of the amount of binder on adhesion properties of zeolite coatings was first investigated to determine the optimum ratio between zeolite and binder. Zeolite coatings were then elaborated with a high zeolite content (between 70 and 80 wt.%) to ensure high adsorption capacities. The amount of binders involved in different zeolite coatings was sufficient to achieve interesting adhesion and cohesion properties. The accessibility of zeolite microporosity was studied by nitrogen adsorption-desorption measurements, which revealed a very small or no loss of the micropore volume for the optimized coatings. Volatile Organic Compounds (VOCs) adsorption measurements were carried out using n-hexane as probe molecule. FAU-type zeolite in powder form adsorbs 180 mg/ganhydrous zeolite, whereas the amounts of n-hexane adsorbed by zeolite coatings ranged from 131 to 175 mg/ganhydrous zeolite. [ABSTRACT FROM AUTHOR]

Binderless pure silica zeolites (zeosils) spheres and hollow spheres with a diameter of 20 µm composed of silicalite-1 nanosheets particles were prepared by pseudomorphic transformation of spherical silica beads using different temperatures (110, 130, and 150 °C) and treatment times (1–5 days) in order to adapt the local dissolution rate of silica to the crystallization rate of silicalite-1 nanosheets allowing to preserve the initial morphology of the silica beads. Fully crystalline beads of 20 µm were obtained at 110 °C for 5 days, whereas hollow spheres similar in size were synthesized at higher temperatures. The crystallization process seems to begin at the outer surface of the amorphous silica beads and spreads with the time in the interior of the beads leading to a dissolution of the inner amorphous part of the beads to create zeosil hollow spheres for the highest treatment temperatures (130 and 150 °C). The dissolution rate of the inner amorphous part of the beads increases by increasing the hydrothermal treatment temperature from 130 to 150 °C. The silicalite-1 beads synthesized at 110 °C for 5 days showed to be promising for rapid molecular decontamination by adsorbing n-hexane in larger amount than the silicalite-1 conventional big crystals in powder forms. [ABSTRACT FROM AUTHOR]