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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]

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]

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]

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]

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]

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 g-1). The results of a high-resolution transmission electron microscopy study suggest HPM-5 may be far more complicated than "standard" layered zeolites and may consist of low-density layers profusely decorated by holes. The resulting lace-like layers may be too unstable to withstand reactions characteristic of more conventional layered materials (both delamination and expansion by silylation); although the derivatives show an increase in the specific surface area, the layers are apparently disassembled and, at most, only ribbons remain. [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]