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International audience; The interest for the environmental, industrial and technological applications of Si-rich zeolites is very high. Among the large-pore zeolites, faujasite is one of the most exploited. The aim of this paper is to obtain detailed structural information on natural and NH4 -exchanged faujasite before using this zeolite for dealumination tests, targeting the realization of large single crystals of allsilica faujasite. As one of the most Si-rich natural samples, faujasite from Sasbach (Na13.64 K0.87 Mg10.46 Ca8.89 Sr0.34 (Al51.95 Si139.57 ) O384 ·272.29 H2 O; space group Fd-3 m; a = 24.6906(2) Å) was chosen for study. Single-crystal X-ray diffraction structural refinements of both natural and NH4 -exchanged samples are reported and discussed. In the natural faujasite sample, almost all the extraframework species could be located for the first time. In the NH4 -exchanged sample the ammonium and water molecule sites were located. Ammonium cations occupy two of the sites occupied by the extraframework species in the original mineral.

This paper reports a study, performed by in-situ synchrotron X-ray powder diffraction, of the high-pressure behavior of zeolite L. The experiments were performed using both penetrating (methanol: ethanol: water mixture, m.e.w.) and non-penetrating (silicon oil, s.o.) pressure transmitting media (PTM) to study the compressibility and the possible pressure-induced hydration (PIH) of this synthetic zeolite, technologically relevant as host-guest system exploited in numerous application fields. The experiments were performed from Pamb to 6.2 and 6.3 GPa in s.o. and m.e.w., respectively. The crystal structure refinements were performed up to 6.3 GPa and 3.1 GPa for the patterns collected in m.e.w. and s.o., respectively, while the unit cell parameters were determined in the whole pressure range for both media. A strong PIH effect is evident when zeolite L is compressed in m.e.w. and the over-hydration is essentially ascribable to the filling of most the H2O sites, to the appearance of a new H2O site and to the partially filling of the K sites. The over-hydration starts at a very low pressure (0.5 GPa) and the maximum H2O content can be estimated in 31.1 H2O molecules, against the original value of 18. The PIH is completely reversible upon P release. The main difference between the compression behavior of zeolite L in the two media is the higher compressibility in the non-penetrating one, evidenced by ΔV = − 6.3% and −9.9% in m.e.w. and s.o, respectively. Our data are consistent with the general behavior of zeolites compressed with penetrating media, when the intrusion of H2O molecules hinders the effects of the applied pressure. The results of this work are compared with those obtained on a K-gallosilicate with LTL topology, where PIH induces the formation of H2O nanotubes inside the zeolite channel.

We present the results of a study on the thermal stability and dehydration dynamics of the porous aluminophosphate AlPO4-5, from room temperature to 850 °C, carried out by in situ synchrotron X-ray powder diffraction experiments. No phase transitions were observed in the investigated T range. Due to the very low interactions among framework and water molecules, dehydration is already complete at 152 °C. It occurs in two main T ranges, one between 60 and 80 °C and the second one between 90 and 120 °C. During these two stages, the cell volume tends to increase to facilitate the water release. Overall, across the full explored T range, the cell volume increase is only 0.84%, indicating that AlPO4-5 is one of the most rigid zeolite frameworks studied to date. Specifically, after complete dehydration at 200 °C, AlPO4-5 undergoes a negative thermal expansion as a consequence of the decrease in both a and c cell parameters. The expansion coefficients for V, a and c cell parameters, in the 152–850 °C range, are αV = −7.12 (10−6/K), αa = −2.5 (10−6/K), αc = −2.2 (10−6/K), respectively.

Organic/inorganic hybrid materials - like zeolites + dyes - are currently used in strategic areas, from sustainable energy technologies to biomedical sciences. In these systems, photoactive molecules are organized in one-dimensional nanostructures inside the zeolite channels. In this paper we present the results of a study aimed to the synthesis and the structural and spectroscopic characterization of azobenzene/AlPO4-5 hybrid composites, performed by a multi-technique approach based on material synthesis, thermal gravimetric analysis, synchrotron X-ray powder diffraction, UV-VIS and IR spectroscopies. The results indicate that azobenzene molecules are hosted in the 12-membered ring channel of AFI framework and the maximum loading is 0.9 molecules per unit cell. The combination of spectroscopic and diffractometric methods point out that, being AlPO4-5 starting material affected by Bronsted acidity, a consistent portion of the azobenzene molecules is protonated and interact with the framework oxygen atoms.

Turning disorder into organization is a key issue in science. By making use of X-ray powder diffraction and modeling studies, we show herein that high pressures in combination with the shape and space constraints of the hydrophobic all-silica zeolite ferrierite separate an ethanol–water liquid mixture into ethanol dimer wires and water tetramer squares. The confined supramolecular blocks alternate in a binary two-dimensional (2D) architecture that remains stable upon complete pressure release. These results support the combined use of high pressures and porous networks as a viable strategy for driving the organization of molecules or nano-objects towards complex, pre-defined patterns relevant for the realization of novel functional nanocomposites.

Within the framework of a project aimed to develop protective coatings for antique glass windows, three glass varieties of medieval-like composition were prepared using recipes deduced from archaeometric studies and different amounts of potassium for fluxing (15–20–25 K 2 O wt.%). Batches were melted in mullite crucibles using an electric furnace at 1350 °C, the glass was fast cooled in air and annealed at temperatures 20 °C higher than the sample glass transition temperatures (726, 702 and 683 °C for V1, V2 and V3, respectively). The chemical composition of the glass was determined by X-Ray Fluorescence Spectroscopy (XRF) and the glass transition temperature was checked by differential thermal analysis (DTA). X-Ray Powder Diffraction (XRPD) data and vibrational spectroscopic experiments (FT-IR and Raman) revealed a direct dependence of glass de-polymerization on potassium content. In particular, the Raman data were interpreted on the basis of SiO 4 structural units Q n and the polymerization index I p .

This is a comparative study on the high-pressure behavior of microporous materials with an MFI framework type (i.e.natural mutinaite, ZSM-5 and the all-silica phase silicalite-1), based onin-situexperiments in which penetrating and non-penetrating pressure-transmitting media were used. Different pressure-induced phenomena and deformation mechanisms (e.g.pressure-induced over-hydration, pressure-induced amorphization) are discussed. The influence of framework and extra-framework composition and of the presence of silanol defects on the response to the high pressure of MFI-type zeolites is discussed.