Ion exchange capacity of synthetic zeolite L: a promising way for cerium recovery.

The increasing rare earth elements' (REE) demand to meet the market request and the current political scenario show that it is essential to find good solutions to recover these elements from waste (both industrial and mining). Zeolites are microporous materials with high cation exchange capacity, up to now only little investigated for REE recycle. Here, we propose the use of NH4+-exchanged zeolite L for Ce recovery from a very diluted solution (0.002 M), mimicking the Ce3+ concentration of the liquors deriving from the leaching of spent catalysts. The aim of this work is twofold: (i) to investigate the exploitability of zeolite L as cation exchanger in the Ce recovery; and (ii) to determine the best working conditions. The investigated process consists of a coupled cation exchange: (1) in the first exchange the NH4+ cations - present in the zeolite porosities - are exchanged with the Ce3+ ions in the solution; and (2) in the second experiment, the Ce3+ trapped into the zeolite is recovered through a further exchange with NH4. The best working conditions for Ce3+ exchange of NH4-zeolite L are: batch system, liquid/solid ratio equal to 90 mL/g and 180 mL/g, 24 h of contact at 25 °C. The resulting Ce adsorption capacity (qt) is equal to ~25 mg/g and ~39 mg/g and the removal efficiency 100% and 77% for the two tested liquid/solid ratios, respectively. The kinetics was proved to be fast and consistent with industrial timing; no energy cost for temperature setting is required; and the acid pH (~4) of the solutions does not affect the zeolite structure stability and its exchange performance. It has been demonstrated that the zeolite framework is not affected by the exchange so that the same absorbent material can be employed many times.

Amino acid encapsulation in zeolite MOR: Effect of spatial confinement.

In this study the absorption of glycine, α-alanine and ß-alanine amino acids into the pores of the synthetic zeolite Na-mordenite was investigated with the aim of: (i) evaluating the effectiveness of the MOR framework type in amino acid adsorption (via vapor and aqueous loading); (ii) understanding the host-guest and guest-guest interactions to possibly design a tailor made material and a loading procedure able to maximize the amino acid adsorption; (iii) studying the effect of pressure on the adsorbed amino acids such as, for instance, possible amino acid condensation. The structural characterization, carried out with the combination of diffractometric and infrared spectroscopy analyses, shows that MOR can adsorb amino acids, which are found both in protonated/deprotonated (possibly also generating zwitterions) form. Vapor loading is ineffective for α-alanine, while it is effective in ß-alanine and glycine adsorption, even if using different loading degrees. The shape and size of MOR channels make this zeolite suitable to accommodate a peptide. In a glycine loaded sample some molecules condensate to form cyclic dimers, while linear oligomers are detected only in a ß-alanine MOR hybrid. The sample loaded with α-L-alanine from aqueous solution does not show the presence of amide bond signals, indicating that the molecules are mostly hosted in zwitterionic form in Na-MOR channels. The application of external baric stimuli does not induce substantial modifications in the structure of the glycine loaded zeolite; this result may be explained by the low number of molecules hosted in the channels. The amino acid amount within the zeolite pores is the most important reactivity parameter and an increased loading could induce chemical modifications.

Structural interpretation of the energetic performances of a pure silica LTA-type zeolite.

The high pressure intrusion-extrusion process of different electrolyte aqueous solutions (NaCl and CaCl2, 2 M and 3 M) in a hydrophobic pure-silica LTA zeolite was investigated for energetic purposes by means of in situ X-ray powder diffraction, porosimeter tests, thermogravimetric analysis and NMR spectroscopy. The intrusion pressure of the saline solutions was proved to be higher than that of pure water, with the highest value measured for CaCl2, thus increasing the energetic performance of the system. The intrusion of NaCl solutions was irreversible (bumper behavior), whereas that of CaCl2 solutions is partially reversible (shock absorber behavior). The structural investigation allowed interpreting these results on the basis of the different intrusion mechanisms, in turn induced by the different nature of the cations present in the electrolyte solutions. When Si-LTA is intruded by NaCl solution, firstly H2O molecules penetrate the pores, leading to higher silanol defect formation followed by the solvated ions. With CaCl2, instead, due to a higher solvation enthalpy of Ca2+, a higher pressure is required for intrusion, and both H2O and ions penetrate at the same pressure. The structural refinements demonstrate (i) a different arrangement of the extraframework species in the two systems, (ii) the intrusion of the salt solutions occurs through strong desolvation of the ions and (iii) the salt/H2O ratios of the intruded species are higher than those of the starting electrolyte solutions.

High-temperature behavior of natural ferrierite: In-situ synchrotron X-ray powder diffraction study.

In this paper, we report the results of the first study focused on the thermal stability and dehydration dynamics of the natural zeolite mineral ferrierite. A sample from Monastir, Sardinia [(Na0.56K1.19Mg2.02Ca0.52Sr0.14) (Al6.89Si29.04)O72·17.86H2O; a = 19.2241(3) Å; b = 14.1563(2) Å; c = 7.5106(1) Å, V = 2043.95(7) Å3] was investigated by thermogravimetric analysis and in-situ synchrotron X-ray powder diffraction. Thermogravimetric data show that H2O release begins already in the range 50-100 °C and is complete at ~600 °C. The results of the structure refinements performed in Immm space group by Rietveld analysis with data collected up to 670 °C show that ferrierite belongs to the group of zeolites that do not undergo phase transitions. Upon heating to 670 °C, ferrierite behaves as a non-collapsible structure displaying only a slight contraction of the unit-cell volume (ΔV = -3%). The unit-cell parameter reductions are anisotropic, more pronounced for a than for b and c (Δa = -1.6%; Δb = -0.76%; Δc = -0.70%). This anisotropic response to a temperature increase is interpreted as due to the presence in the ferrierite framework of five-membered ring chains of SiO4 tetrahedra, which impart a higher structural rigidity along b and c. Upon dehydration we observe: (1) the gradual H2O loss, beginning with the molecules hosted in the 10MR channel, is almost complete at 670 °C, in good agreement with the TG data; (2) as a consequence of the decreased H2O content, Mg and K migrate from their original positions, moving from the center of the 10MR channel toward the walls to coordinate the framework oxygen atoms. The observation of transmission electron microscopy selected-area electron diffraction patterns revealed defective crystals with an occasional and moderate structural disorder. Beyond providing information on the thermal stability and behavior of natural ferrierite, the results of this work have significant implications for possible technological applications. These data allow for comparison with the dehydration kinetics/mechanisms of the corresponding synthetic phases, clarifying the role played by framework and extra-framework species on the high-temperature behavior of porous materials with ferrierite topology. Moreover, the information on the thermal behavior of natural ferrierite can be used to predict the energetic performances of analogous synthetic Si-pure counterparts, namely "zeosil-electrolyte" systems, under non-ambient conditions. Specifically, the very high thermal stability of ferrierite determined in this study, coupled with the baric behavior determined in other investigations, suggests that the "Si-FER-electrolyte" system may be an excellent candidate for use as an energy reservoir. Indeed, ferrierite exhibits the so-called "spring behavior," i.e., upon compression in water or in an electrolyte solution, it converts the mechanical energy into interfacial energy, and-when pressure is released-it can completely restore the supplied mechanical energy accumulated during the compression step.

Irreversible Conversion of a Water-Ethanol Solution into an Organized Two-Dimensional Network of Alternating Supramolecular Units in a Hydrophobic Zeolite under Pressure.

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.

High-pressure-induced structural changes, amorphization and molecule penetration in MFI microporous materials: a review.

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 on in-situ experiments 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.