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[EN] 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

Stacking faults are two-dimensional planar defects frequently arising in zeolites, modifying their properties and potentially affecting their performance in catalysis and separation applications. In classical zeolite intergrowths, a topologically unique zeolite layer may often pile up after some spatial transformation (lateral translation, rotation, and/or reflection) that may occur in different amounts or directions with about similar probabilities, leading to a difficult to control disorder. Here, we present a new kind of zeolite intergrowth that requires an additional topologically distinct layer rather than a spatial transformation of a unique one. Stacking of the so-called pentasil layers produces the well-known medium pore zeolite MFI. Intercalation in strict alternation of a topologically distinct second layer sandwiched between pentasil layers expands the structure to produce the new extra-large pore IDM-1. Stacking disorder modulates the structural expansion along the stacking direction. The disordered materials have been studied by simulation of the X-ray diffraction patterns using the program DIFFaX and by Cs-corrected high-resolution electron microscopy. We show that disorder does not occur at random but in extended domains and can be controlled all the way from MFI to IDM-1 by just varying the concentration of the synthesis mixture., QC 20211110

Stacking faults are two-dimensional planar defects frequently arising in zeolites, modifying their properties and potentially affecting their performance in catalysis and separation applications. In classical zeolite intergrowths, a topologically unique zeolite layer may often pile up after some spatial transformation (lateral translation, rotation, and/or reflection) that may occur in different amounts or directions with about similar probabilities, leading to a difficult to control disorder. Here, we present a new kind of zeolite intergrowth that requires an additional topologically distinct layer rather than a spatial transformation of a unique one. Stacking of the so-called pentasil layers produces the well-known medium pore zeolite MFI. Intercalation in strict alternation of a topologically distinct second layer sandwiched between pentasil layers expands the structure to produce the new extra-large pore IDM-1. Stacking disorder modulates the structural expansion along the stacking direction. The disordered materials have been studied by simulation of the X-ray diffraction patterns using the program DIFFaX and by Cs-corrected highresolution electron microscopy. We show that disorder does not occur at random but in extended domains and can be controlled all the way from MFI to IDM-1 by just varying the concentration of the synthesis mixture.

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 degrees 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.

[EN] 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)(OH) and Si(OSi)(OH) 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 SiO and hydrophilic SiO(OH) 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.

[EN] The synthesis of zeolites with new structures and/or improved properties heavily relies on trial and error efforts that are not entirely blind, as the large empirical background accumulated for the last 7 decades can be, to some extent, rationalized and purposefully used to make new materials. The so-called structure-directing factors may be combined to promote (or frustrate) the crystallization of a particular structure. This personal account opens with the concept of geoinspiration, as suggested by Prof. Ruiz-Hitzky, and its application to zeolite synthesis. We then provide a concise overview of structure-direction in the synthesis of zeolites and detail examples, both new and from the literature, on how they can be combined to drive the crystallization towards (or away from) structures displaying particular features.

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 GeO 2 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.

Calcination in air of GeO 2 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 N 2 , 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 N 2 : for tetramethylammonium the residue is GeO 2 while trimethyl-terc-butylammonium, thanks to its larger C content, yields metallic Ge. Framework organoreduction is not unique to GeO 2 -AST zeolites but also occurs during the calcination in air of other germanium-containing zeolites with larger pore openings.

There is large interest in replicating biological supramolecular structures in inorganic materials that are capable of mimicking biological properties. The use of 5-guanosine monophosphate in the presence of Na+ and K+ ions as a supramolecular template for the synthesis of well-ordered mesostructured materials is reported here. Mesostructured particles with the confined template exhibit high structural order at both meso-and atomic scales, with a lower structural symmetry in the columnar mesophase. Although a chiral space group can not be deduced from X-ray diffraction, analysis by electron microscopy and circular dichroism confirms a chiral stacking arrangement along the c-axis. Guanosine monophosphate based mesophases thus illustrate the possibility for specific molecular imprinting of mesoporous materials by genetic material and the potential for higher definition in molecular recognition., AuthorCount:3

A method to form ordered mesoporous silica based on the use of folate supramolecular templates has been developed. Evidence based on in situ small-angle X-ray scattering (SAXS), electron microscopy, infrared spectroscopy, and in situ conductivity measurements are used to investigate the organic-inorganic interactions and synthesis mechanism. The behavior of folate molecules in solution differs distinctively from that of surfactants commonly used for the preparation of ordered mesoporous silica phases, notably with the absence of a critical micellar concentration. In situ SAXS studies reveal fluctuations in X-ray scattering intensities consistent with the condensation of the silica precursor surrounding the folate template and the growth of the silica mesostructure in the initial stages. High-angle X-ray diffraction shows that the folate template is well-ordered within the pores even after a few minutes of synthesis. Direct structural data for the self-assembly of folates into chiral tetramers within the pores of mesoporous silica provide evidence for the in register stacking of folate tetramers, resulting in a chiral surface of rotated tetramers, with a rotation angle of 30°. Additionally, the self-assembled folates within pores were capable of adsorbing a considerable amount of CO2 gas through the cavity space of the tetramers. The study demonstrates the validity of using a naturally occurring template to produce relevant and functional mesoporous materials.