Calorimetric Heats of Intrusion of LiCl Aqueous Solutions in Hydrophobic MFI-Type Zeosil: Influence of the Concentration.

For the first time, we report calorimetric measurements of intrusion of aqueous LiCl solutions in a hydrophobic pure siliceous MFI zeolite (silicalite-1) under high pressure. Our results show that the intrusion heats are strongly dependent on the LiCl concentration. The intrusion process is endothermic for diluted solutions (molar H2O/LiCl = 12) as well as for water, but it becomes exothermic for a concentration close to saturation (molar H2O/LiCl = 4). Analysis of the data in the framework of wetting thermodynamics shows that besides surface wetting, other phenomena occur during intrusion, such as hydrogen-bond weakening and composition change. In all cases, water is preferentially intruded so that the intruded phase becomes more diluted than the bulk solution. In the case of the most diluted solution, only water molecules seemed to be intruded. Furthermore, silicalite-1 is shown to be very stable in the presence of LiCl solution, with no noticeable structural and textural modifications observed after intrusion.

Zeolite/Polymer Composites Prepared by Photopolymerization: Effect of Compensation Cations on Opacity and Gas Adsorption Applications.

The fabrication of structured zeolite adsorbents through photopolymerization-based 3D printing which offers a solution to the limitations of conventional shaping techniques has been demonstrated but many parameters still need to be optimized. In this study, we studied the influence of zeolite compensation cations on the photopolymerization and the composite's properties. Modified zeolites (LTA 4 A and FAU 13X exchanged with K+ , Li+ , Sr2+ , Ca2+ or Mg2+ ) were incorporated in PEGDA with BDMK as photoinitiator, and the formulation was cured under mild conditions (LED@405 nm, room temperature, under air). Our results indicate that the nature of zeolite compensation cations affects the colorimetric properties of polymer/zeolite composites: a better translucency parameter results in higher depth of cure. After calcination at 650 °C and complete removal of PEGDA, pure zeolitic monoliths were tested for adsorption of gas molecules of interest (carbon dioxide, dichlorobenzene and water). Structured 4 A and 13X monoliths obtained by 3D printing exhibit comparable adsorption capacity to commercial beads prepared from the same zeolites. This study enhances our understanding of the photopolymerization process involved in the production of polymer/zeolite composites. These composites are used in the fabrication of zeolitic objects through 3D printing, offering potential solutions to various environmental and dental challenges.

Rational Design and Characterisation of Novel Mono- and Bimetallic Antibacterial Linde Type A Zeolite Materials.

The development of antimicrobial devices and surfaces requires the setup of suitable materials, able to store and release active principles. In this context, zeolites, which are microporous aluminosilicate minerals, hold great promise, since they are able to serve as a reservoir for metal-ions with antimicrobial properties. Here, we report on the preparation of Linde Type A zeolites, partially exchanged with combinations of metal-ions (Ag+, Cu2+, Zn2+) at different loadings (0.1-11.9 wt.%). We combine X-ray fluorescence, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray diffraction to monitor the metal-ion contents, distribution, and conservation of the zeolite structure after exchange. Then, we evaluate their antimicrobial activity, using agar dilution and optical-density monitoring of Escherichia coli cultures. The results indicate that silver-loaded materials are at least 70-fold more active than the copper-, zinc-, and non-exchanged ones. Moreover, zeolites loaded with lower Ag+ concentrations remain active down to 0.1 wt.%, and their activities are directly proportional to the total Ag content. Sequential exchanges with two metal ions (Ag+ and either Cu2+, Zn2+) display synergetic or antagonist effects, depending on the quantity of the second metal. Altogether, this work shows that, by combining analytical and quantitative methods, it is possible to fine-tune the composition of bi-metal-exchanged zeolites, in order to maximise their antimicrobial potential, opening new ways for the development of next-generation composite zeolite-containing antimicrobial materials, with potential applications for the design of dental or bone implants, as well as biomedical devices and pharmaceutical products.

Zeolite-Polymer Composite Materials as Water Scavenger.

The influence of the charge compensating cation nature (Na+, Mg2+) on the water adsorption properties of LTA-type zeolites used as filler in composite materials (zeolite/polymers) was investigated. Large scale cation exchanges were performed on zeolite powder at 80 °C for 2 h using 1 M magnesium chloride (MgCl2) aqueous solutions. XRF, ICP, and EDX analyses indicate a successful cationic exchange process without the modification of the zeolite structure as shown by XRD and solid-state NMR analyses. Composite materials (granulates and molded parts) were manufactured using to extrusion and injection processes. In the case of MgA zeolite, nitrogen adsorption-desorption experiments allowed us to measure a microporous volume, unlike NaA zeolite, which is non-porous to nitrogen probe molecule. SEM and EDX analyses highlighted the homogeneous distribution of zeolite crystals into the polymer matrix. Water adsorption capacities confirmed that the trends observed in the zeolite powder samples are preserved after dragging zeolites into composite formulations. Granulates and molded parts composite samples containing the magnesium exchanged zeolite showed an increase of their water adsorption capacity up to +27% in comparison to composite samples containing the non-exchanged zeolite. The MgA composite is more promising for water decontamination applications due to its higher water adsorption properties than the NaA composite.

Synthesis of FAU-Type Zeolite Membranes with Antimicrobial Activity.

In this study, a layer of a pure and dense phase of FAU-type zeolite was synthesized directly on the surface of α-Al2O3 plane macroporous support. Before hydrothermal synthesis, a step of cleaning of the support by an anionic detergent was performed, a roughness surface is created, allowing the anchoring of the zeolite nuclei and then their growth, favoring in this sense the formation of a homogeneous zeolite layer. The obtained membranes were fully characterized using X-ray diffraction analysis (XRD), nitrogen sorption, scanning electron microscopy (SEM), and mercury porosimetry. After 24 h of thermal treatment at 75 °C, a homogeneous zeolite layer composed of bipyramidal crystals of FAU-type zeolite is obtained with a thickness of about 2.5 µm. No obvious defects or cracks can be observed. It was found that the increase in heating temperature could lead to the appearance of an impurity phase, GIS-type zeolite. Then the ideal zeolite membrane was exchanged with Ag+ or Zn2+ cations to studies their antimicrobial properties. Zeolites membranes exchanged with Ag+ showed an agar-diffusive bactericidal activity against gram negative Escherichia coli (E. coli) bacteria. Zn2+ exchanged zeolite membrane presented a bacteriostatic activity that is less diffusive in agar. As expected, non-exchanged zeolite membrane (in its Na+ form) have no effect on bacterial activity. This process is particularly interesting for the synthesis of a good quality FAU-type zeolite membranes with antimicrobial properties.

Efficient Removal of Volatile Organic Compounds by FAU-Type Zeolite Coatings.

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.

Energetic Performance of Pure Silica Zeolites under High-Pressure Intrusion of LiCl Aqueous Solutions: An Overview.

An overview of all the studies on high-pressure intrusion-extrusion of LiCl aqueous solutions in hydrophobic pure silica zeolites (zeosils) for absorption and storage of mechanical energy is presented. Operational principles of heterogeneous lyophobic systems and their possible applications in the domains of mechanical energy storage, absorption, and generation are described. The intrusion of LiCl aqueous solutions instead of water allows to considerably increase energetic performance of zeosil-based systems by a strong rise of intrusion pressure. The intrusion pressure increases with the salt concentration and depends considerably on zeosil framework. In the case of channel-type zeosils, it rises with the decrease of pore opening diameter, whereas for cage-type ones, no clear trend is observed. A relative increase of intrusion pressure in comparison with water is particularly strong for the zeosils with narrow pore openings. The use of highly concentrated LiCl aqueous solutions instead of water can lead to a change of system behavior. This effect seems to be related to a lower formation of silanol defects under intrusion of solvated ions and a weaker interaction of the ions with silanol groups of zeosil framework. The influence of zeosil nanostructure on LiCl aqueous solutions intrusion-extrusion is also discussed.

Influence of the Compensating Cation Nature on the Water Adsorption Properties of Zeolites.

The influence of the compensating cation (Na+, Li+, Mg2+) nature on the water adsorption properties of LTA and FAU-type zeolites was investigated. Cation exchanges were performed at 80 °C for 2 h using 1 M aqueous solutions of lithium chloride (LiCl) or magnesium chloride (MgCl2). XRF and ICP-OES analyses indicate that the cation exchange yields reach values between 59 to 89% depending on the number of exchange cycles and the nature of the zeolite and cation, while both zeolites structures are preserved during the process, as shown by XRD and solid state NMR analyses. Nitrogen adsorption-desorption experiments indicate a higher available microporous volume when sodium cations are replaced by smaller monovalent lithium cations or by divalent magnesium cations because twice less cations are needed compared to monovalent cations. Up to 15% of gain in the available microporous volume is obtained for FAU-type zeolites exchanged with magnesium cation. This improvement facilitates the adsorption of water with an increase in the water uptake up to 30% for the LTA and FAU type zeolites exchanged with magnesium. These exchanged zeolites are promising for uses in water decontamination because a smaller amount is needed to trap the same amount of water compared to their sodium counterparts.

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.

Modeling SOx trapping on a copper-doped CuO/SBA-15 sorbent material.

A mixture of SO2 and air was continuously injected in a fixed bed reactor containing a CuO/SBA-15 sorbent material and submitted to an isothermal temperature between 325 and 400 °C. The SO2 emissions were measured at the exit of the reactor. Different isothermal temperatures, different injected SO2 concentrations and different sorbent masses, all representative of industrial conditions, were tested. The purpose of the paper was to propose efficient global models which simulate the breakthrough curves whatever the experimental conditions. A simplified model was first considered assuming that the oxidation and trapping processes can occur on each copper site. The values of the four kinetic parameters which are involved were determined solving this model using Scilab software and an optimization routine. Because this model failed to reproduce in a satisfying way the breakthrough curves for different sorbent masses, a second model was introduced which involves surface and bulk trapping sites and six kinetic parameters. The breakthrough curves simulated with this second model following the same resolution techniques were in better agreement with the experimental ones, whatever the experimental conditions. For comparison, a simulation of the breakthrough curves returned by a model with bulk diffusion was presented.

Binary Oxides Prepared by Microwave-Assisted Solution Combustion: Synthesis, Characterization and Catalytic Activity.

Three different alumina-based Ni, Cu, Co oxide catalysts with metal loading of 10 wt %, and labeled 10Ni⁻Al, 10Co⁻Al and 10Cu⁻Al, were prepared by microwave-assisted solution combustion. Their morphological, structural and surface properties were deeply investigated by complementary physico-chemical techniques. Finally, the three materials were tested in CO oxidation used as test reaction for comparing their catalytic performance. The 10Cu⁻Al catalyst was constituted of copper oxide phase, while the 10Ni⁻Al and 10Co⁻Al catalysts showed the presence of "spinels" phases on the surface. The well-crystallized copper oxide phase in the 10Cu⁻Al catalyst, obtained by microwave synthesis, allowed for obtaining very high catalytic activity. With a CO conversion of 100% at 225 °C, the copper containing catalyst showed a much higher activity than that usually measured for catalytic materials of similar composition, thus representing a promising alternative for oxidation processes.

Performance of surfactant-modified *BEA-type zeolite nanosponges for the removal of nitrate in contaminated water: Effect of the external surface.

Hierarchical *BEA-type nanosponges zeolite with a high external surface area (116 m2.g-1) and small crystal size, synthesized in the presence of a dual-porogenic organic compound, were modified with a cationic surfactant (HDTMA+Br-: hexadecyltrimethyl ammonium bromide) in order to create a new anion exchanger system: the surfactant-modified zeolite nanosponges (SMZNS). For comparison, two other surfactant-modified *BEA-type zeolite materials, SMZMC and SMZNC, were obtained by modifying the synthesized conventional micron-size microcrytals and nanocrystals *BEA-type zeolite with HDTMA+Br-, respectively. Textural and structural properties were determined for the three prepared materials using N2 adsorption/desorption analysis, XRD, SEM, and TEM. Nitrate adsorption isotherms were drawn in a large concentration range [0.8-24.2 mmol.L-1] and fitted with Langmuir isotherm model. The maximum nitrate removal capacity (1338 mmol.Kg-1/83 mg.g-1) was obtained for SMZNS material. This value is the highest ever observed for nitrate removal using surfactant-modified zeolite. The nitrate removal kinetics were fitted with the pseudo second-order model for both materials SMZNS and SMZNC.

Synthesis of Binderless ZK-4 Zeolite Microspheres at High Temperature.

Binderless zeolite macrostructures in the form of ZK-4 microspheres were prepared using anion-exchange resin beads as shape-directing macrotemplates. The particles were synthesized under hydrothermal conditions at different temperatures and treatment times. The influence of the different synthesis parameters was investigated by X-ray diffraction, scanning electron microscopy, fluorescence X, nitrogen adsorption measurements and 29Si solid-state NMR. Fully crystalline spheres similar in size and shape to the original resin beads were obtained by a hydrothermal treatment at the highest temperatures (150⁻180 °C) for a short treatment time of 24 h. The synthesized microspheres showed to be promising in the molecular decontamination of volatile organic compounds (VOCs).

Porous sorbents for the capture of radioactive iodine compounds: a review.

The number of studies on the capture of radioactive iodine compounds by porous sorbents has regained major importance in the last few years. In fact, nuclear energy is facing major issues related to operational safety and the treatment and safe disposal of generated radioactive waste. In particular during nuclear accidents, such as that in 2011 at Fukushima, gaseous radionuclides have been released in the off-gas stream. Among these, radionuclides that are highly volatile and harmful to health such as long-lived 129I, short-lived 131I and organic compounds such as methyl iodide (CH3I) have been released. Immediate and effective means of capturing and storing these radionuclides are needed. In the present review, we focus on porous sorbents for the capture and storage of radioactive iodine compounds. Concerns with, and limitations of, the existing sorbents with respect to operating conditions and their capacities for iodine capture are discussed and compared.

Intrusion-extrusion spring performance of -COK-14 zeolite enhanced by structural changes.

-COK-14 zeolite, the variant of COK-14 (OKO topology) with a systematically interrupted framework, exhibits unusual behaviour in high pressure intrusion-extrusion cycles of 20 M LiCl solution. After the first cycle with deviating behaviour and partially irreversible intrusion, subsequent cycles show stable reversible behaviour. The system behaves like a spring with unique progressive intrusion in the range of 10-120 MPa followed by enhanced uptake before saturation. While the intrusion-extrusion cycling leads to fragmented crystals, powder diffraction reveals high crystallinity of the fragments. Based on the detailed characterisation of the zeolite samples with XRD, Rietveld refinement, N2 adsorption, TGA and (29)Si MAS NMR before and after intrusion-extrusion experiments, a model of the structure of the intruded -COK-14 samples is proposed. Intrusion-extrusion of LiCl solution systematically breaks the most strained bonds in the structure which results in a new framework connectivity with enhanced stability, which persists during the harsh intrusion-extrusion conditions.

Characterisation and seasonal variations of particles in the atmosphere of rural, urban and industrial areas: Organic compounds.

Atmospheric aerosol samples (PM2.5-0.3, i.e., atmospheric particles ranging from 0.3 to 2.5µm) were collected during two periods: spring-summer 2008 and autumn-winter 2008-2009, using high volume samplers equipped with cascade impactors. Two sites located in the Northern France were compared in this study: a highly industrialised city (Dunkirk) and a rural site (Rubrouck). Physicochemical analysis of particulate matter (PM) was undertaken to propose parameters that could be used to distinguish the various sources and to exhibit seasonal variations but also to provide knowledge of chemical element composition for the interpretation of future toxicological studies. The study showed that PM2.5-0.3 concentration in the atmosphere of the rural area remains stable along the year and was significantly lower than in the urban or industrial ones, for which concentrations increase during winter. High concentrations of polycyclic aromatic hydrocarbons (PAHs), dioxins, furans and dioxin like polychlorinated biphenyls (DL-PCBs), generated by industrial activities, traffic and municipal wastes incineration were detected in the samples. Specific criteria like Carbon Preference Index (CPI) and Combustion PAHs/Total PAHs ratio (CPAHs/TPAHs) were used to identify the possible sources of atmospheric pollution. They revealed that paraffins are mainly emitted by biogenic sources in spring-summer whereas as in the case of PAHs, they have numerous anthropogenic emission sources in autumn-winter (mainly from traffic and domestic heating).

Assessment of the energetic performances of various ZIFs with SOD or RHO topology using high pressure water intrusion-extrusion experiments.

The energetic performances of seven SOD or RHO-topology ZIFs, with zinc or cobalt metal cation (ZIF-8, ZIF-90, Zn(dcim)2-SALE, ZIF-67, ZIF-7, ZIF-71, ZIF-11) were evaluated using water intrusion-extrusion under high pressure. The relationship between the structural parameters (in particular the pore system SOD or RHO, the type of linker, the metal cation nature) and the intrusion pressure was studied to better understand the mechanism of water intrusion and the energetic behaviour for a given ZIF crystal type. "ZIF-8-water", "ZIF-67-water" and "ZIF-71-water" systems display a shock-absorber behaviour. A very important hysteresis for ZIF-71 and a slight difference between the first intrusion-extrusion cycle and the following ones for ZIF-67 were observed. ZIF-8 (SOD) with zinc cation and ZIF-67 (SOD) with cobalt cation display similar intrusion pressures. For ZIF-71 (RHO) material, the stored energy is more than doubled compared to ZIF-8 and ZIF-67 (SOD). This might be related to the topology. No water intrusion was observed after three water intrusion-extrusion cycles, for the ZIF-90 (SOD), Zn(dcim)2-SALE (SOD), ZIF-7 (SOD) and ZIF-11 (RHO) materials. This is explained in term of hydrophilic feature as well as topology and linker effects.

Energetic behavior of the pure silica ITQ-12 (ITW) zeolite under high pressure water intrusion.

Experimental water intrusion-extrusion isotherms were obtained at room temperature on pure silica ITW-type zeolites (ITQ-12 zeosil). The water intrusion is obtained by applying a high hydraulic pressure corresponding to the intrusion step. When the pressure is released, the water extrusion occurs at a similar pressure to that of the intrusion one. Therefore, the "ITW zeosil-water" system behaves like a spring and the phenomenon is reproducible over several cycles. Several characterization techniques have been performed before and after water intrusion-extrusion experiments in order to reveal the presence or the lack of defects after such experiments. Structural modifications at the long range order cannot be observed by XRD analysis after three water intrusion-extrusion cycles. However, solid state NMR spectroscopy provides evidence of the presence of Q3 groups revealing the breaking of some siloxane bridges after the intrusion step. The "ITW zeosil-water" system can restore 100% of the stored energy corresponding to about 8 J g(-1).

Energetic performances of the metal-organic framework ZIF-8 obtained using high pressure water intrusion-extrusion experiments.

The "ZIF-8-water" system displays reproducible shock-absorber behaviour over several cycles with a stored energy of 13.3 J g(-1) and an energy yield close to 85%. The combination of the main features evidenced for ZIF-8, i.e. a quite low intrusion pressure and a high stored energy, opens a field for new applications.

Nanocrystalline iron oxide synthesised within Hierarchical Porous Silica prepared by nanoemulsion templating.

PIC (Phase Inversion Composition) O-W nanoemulsions was used as a template for the synthesis of Hierarchical Porous Silica (HPS), and the oil phase of the nanoemulsion was used as a nanoreactor for the preparation of magnetic gamma-Fe(2)O(3) nanoparticles, confined within the silica matrix.