Adsorption of radon on silver exchanged zeolites at ambient temperatures.

Since more than 100 years, the adsorption of the radioactive noble gas radon (222Rn) is performed on activated charcoal at cryogenic temperatures. There is little-if any-progress in the field of radon adsorption at ambient conditions to facilitate the development of simple and compact radon adsorption systems. We report here on the truly remarkable property of the synthetic silver-exchanged zeolites Ag-ETS-10 and Ag-ZSM-5 to strongly adsorb radon gas at room temperature. 222Rn breakthrough experiments in nitrogen carrier gas have shown that these materials exhibit radon adsorption coefficients exceeding 3000 m3/kg at 293 K, more than two orders of magnitude larger than any noble gas adsorbent known to date. Water vapor and carrier gas type were found to strongly influence radon adsorption, practically qualifying these silver exchanged materials as a new class of radon adsorbents. Our results demonstrate that Ag-ETS-10 and Ag-ZSM-5 are materials that show high affinity towards radon gas at ambient temperatures making them candidate materials for environmental and industrial 222Rn mitigation applications. Adsorption systems based on silver loaded zeolites have the potential to replace activated charcoal as material of choice in many radon related research areas by avoiding the necessity of cryogenic cooling.

Polonium behavior following a vacuum window rupture in a lead-bismuth eutectic based accelerator driven system.

Accelerator driven fast nuclear reactors cooled by lead-bismuth eutectic (LBE) are developed for transmuting long-lived radionuclides in spent nuclear fuel. Due to the nature of the coolant, operating the reactor will result in a production of 210Po by neutron capture. Understanding the behavior of this highly radiotoxic nuclide in the event of a failure of the window separating the evacuated proton beam guide from the reactor core is required for safety assessments. The present work aims at acquiring this knowledge by studying the evaporation of polonium from neutron-irradiated LBE and its deposition in a scaled down model of the beam tube. Experimental results along with Monte Carlo simulations indicate that polonium adsorbs as a single species with an adsorption enthalpy of approximately -156 kJ/mol.

Po-Containing Molecules in Fusion and Fission Reactors.

Fission and fusion reactors can only play a role in the future energy landscape if they are inherently safe by design. For some reactor concepts, a major remaining issue is the undesired production of radiotoxic 210Po. To filter out the volatile Po species, information on their molecular composition is needed. An experimental characterization is very challenging due to the large required amount of radioactive Po. An alternative quantum chemistry approach was taken to predict the temperature-dependent stability of relevant diatomic Po-containing molecules. Experimental data on lighter analogue molecules was used to establish a well-founded methodology. The relative occurrence of the Po species was estimated in the cover gas of (i) the lead-bismuth eutectic coolant in the accelerator-driven MYRRHA fission reactor and (ii) the Pb-Li eutectic tritium breeder in the DEMO fusion reactor. In both systems, Po is found to occur mainly as PbPo molecules and atomic Po.

Nucleation and growth of lead oxide particles in liquid lead-bismuth eutectic.

Liquid lead-bismuth eutectic (LBE) is an important candidate to become the primary coolant of future, generation IV, nuclear fast reactors and Accelerator Driven System (ADS) concepts. One of the main challenges with the use of LBE as a coolant is to avoid its oxidation which results in solid lead oxide (PbO) precipitation. The chemical equilibria governing PbO formation are well understood. However, insufficient kinetic information is currently available for the development of LBE-based nuclear technology. Here, we report the results of experiments in which the nucleation, growth and dissolution of PbO in LBE during temperature cycling are measured by monitoring dissolved oxygen using potentiometric oxygen sensors. The metastable region, above which PbO nucleation can occur, has been determined under conditions relevant for the operation of LBE cooled nuclear systems and was found to be independent of setup geometry and thus thought to be widely applicable. A kinetic model to describe formation and dissolution of PbO particles in LBE is proposed, based on Classical Nucleation Theory (CNT) combined with mass transfer limited growth and dissolution. This model can accurately predict the experimentally observed changes in oxygen concentration due to nucleation, growth and dissolution of PbO, using the effective interfacial energy of a PbO nucleus in LBE as a fitting parameter. The results are invaluable to evaluate the consequences of oxygen ingress in LBE cooled nuclear systems under normal operating and accidental conditions and form the basis for the development of cold trap technology to avoid PbO formation in the primary reactor circuit.

Continuous synthesis process of hexagonal nanoplates of P6m ordered mesoporous silica.

Hexagonally ordered mesoporous silica coined COK-12 was synthesized in a continuous process by combining streams of sodium silicate and citric acid/sodium citrate buffered solution of (ethylene oxide)(20)-(propylene oxide)(70)-(ethylene oxide)(20) triblock copolymer (Pluronic P123) from separate reservoirs. COK-12 precipitated spontaneously upon combining both streams at nearly neutral pH and ambient temperature. Stable intermediates of the COK-12 formation process could be prepared by limiting sodium silicate addition. Investigation of these intermediates using small-angle X-ray scattering revealed COK-12 formed via an assembly process departing from spherical uncharged core-shell P123-silica micelles. The sterical stabilization of these micelles decreased upon accumulation of silicate oligomers in their shell. Aggregation of the spherical micelles led to cylindrical micelles, which aligned and adopted the final hexagonal organization. This unprecedentedly fast formation of P6m ordered mesoporous silica was caused by two factors in the synthesis medium: the neutral pH favoring uncharged silicate oligomers and the high salt concentration promoting hydrophobic interactions with surfactant micelles leading to silica accumulation in the PEO shell. The easy continuous synthesis process is convenient for large-scale production. The platelet particle morphology with short and identical internal channels will be advantageous for many applications such as pore replication, nanotube or fiber growth, catalytic functionalization, drug delivery, film and sensor development, and in nano dyes as well as for investigation of pore diffusion phenomena.

Evaluation of ordered mesoporous silica as a carrier for poorly soluble drugs: influence of pressure on the structure and drug release.

Ordered mesoporous silica (OMS) materials are considered a promising drug delivery system for the dissolution enhancement of poorly soluble compounds. The purpose of the present work was to determine structural and behavioral changes of compressed OMS material necessary for the development of an immediate-release oral-dosage formulation. Two types of OMS materials (SBA-15 and COK-12) were subjected to pressures both in and beyond the tabletting region and characterized by nitrogen physisorption, scanning and transmission electron microscopy, small-angle X-ray scattering, and differential scanning calorimetry. Itraconazole was used as the poorly soluble model drug and the release process with respect to pressure was determined in vitro. The resulting decreased drug release due to increased pressure was recovered by incorporating a plastically deforming material such as microcrystalline cellulose in combination with croscarmellose sodium. These findings further elucidate the understanding of their structural behavior for the advancement as a drug delivery carrier.

Modelling of synchrotron SAXS patterns of silicalite-1 zeolite during crystallization.

Synchrotron small angle X-ray scattering (SAXS) was used to characterize silicalite-1 zeolite crystallization from TEOS/TPAOH/water clear sol. SAXS patterns were recorded over a broad range of length scales, enabling the simultaneous monitoring of nanoparticles and crystals occurring at various stages of the synthesis. A simple two-population model accurately described the patterns. Nanoparticles were modeled by polydisperse core-shell spheres and crystals by monodisperse oblate ellipsoids. These models were consistent with TEM images. The SAXS results, in conjunction with in situ light scattering, showed that nucleation of crystals occurred in a short period of time. Crystals were uniform in size and shape and became increasingly anisotropic during growth. In the presence of nanoparticles, crystal growth was fast. During crystal growth, the number of nanoparticles decreased gradually but their size was constant. These observations suggested that the nanoparticles were growth units in an aggregative crystal growth mechanism. Crystals grown in the presence of nanoparticles developed a faceted habit and intergrowths. In the final stages of growth, nanoparticles were depleted. Concurrently, the crystal growth rate decreased significantly.

Methods for in situ spectroscopic probing of the synthesis of a zeolite.

Unraveling the crystallization mechanism of zeolites remains an increasingly important challenge in chemistry. During the last decade, in situ spectroscopic methods have provided an unprecedented level of detail of the underlying molecular mechanisms and their kinetics. Magnetic resonance, vibrational and X-ray absorption techniques have emerged as principal tools for the in situ observation of crystallization. In this tutorial review, we discuss how these in situ methods have contributed to our understanding of the complex and diverse molecular processes that govern zeolite crystallization.

Kinetics of intermediate-mediated self-assembly in nanosized materials: a generic model.

We propose in this paper a generic model of a nonstandard aggregation mechanism for self-assembly processes of a class of materials involving the mediation of intermediates consisting of a polydisperse population of nanosized particles. The model accounts for a long induction period in the process. The proposed mechanism also gives insight on future experiments aiming at a more comprehensive picture of the role of self-organization in self-assembly processes.

Hollow filler based mixed matrix membranes.

Micron-sized hollow spheres with zeolitic shell were used as inorganic fillers in PDMS-based mixed matrix membranes, overall enhancing solvent permeabilities as compared to traditional zeolite fillers, while selectivities were maintained.

Direct observation of molecular-level template action leading to self-assembly of a porous framework.

The molecular steps involved in the self-assembly of Cu(3)(BTC)(2) (BTC=1,3,5-benzenetricarboxylic acid) metal-organic frameworks that enclose Keggin-type H(3)PW(12)O(40) heteropolyacid molecules were unraveled by using solution (17)O, (31)P, and (183)W NMR spectroscopy, small-angle X-ray scattering, near-IR spectroscopy, and dynamic light scattering. In aqueous solution, complexation of Cu(2+) ions with Keggin-type heteropolyacids was observed. Cu(2+) ions are arranged around the Keggin structure so that linking through benzenetricarboxylate groups results in the formation of the Cu(3)(BTC)(2) MOF structure HKUST-1. This is a unique instance in which a templating mechanism that relies on specific molecular-level matching and leads to explicit nanoscale building units can be observed in situ during formation of the synthetic nanoporous material.

Growth of itraconazole nanofibers in supersaturated simulated intestinal fluid.

Many drug compounds have limited solubility in water. To enhance the oral bioavailability of such compounds, pharmaceutical formulations target the creation of a supersaturated solution. Release of the compound from ordered mesoporous silica carrier is such a means for reaching supersaturation. Little is known about the evolution of supersaturated intestinal media. The present study reveals the phase transitions of the poorly water-soluble drug itraconazole in simulated intestinal fluid under conditions corresponding to supersaturation. Electron spin resonance of n-doxylstearic acid spin probes evidenced that during supersaturation itraconazole is solubilized inside the hydrophobic core of mixed micelles composed of lecithin and bile salt. Cryogenic transmission electron microscopy revealed that the supersaturated state of itraconazole provokes the formation of nanofibers with a uniform diameter of 12 nm. The nanofiber length determined via dynamic light scattering increases from 220 to 1480 nm after 30 and 90 min, respectively. Nanofibers drastically reduced transepithelial transport of itraconazole across a Caco-2 cell monolayer mimicking the gastrointestinal absorption. Based on our study, we suggest the existence of an optimum intraluminal itraconazole supersaturation at which itraconazole absorption is enhanced but formation of itraconazole nanofibers prevented.

Investigation of the mechanism of colloidal silicalite-1 crystallization by using DLS, SAXS, and 29Si NMR spectroscopy.

Colloidal silicalite-1 zeolite was crystallized from a concentrated clear sol prepared from tetraethylorthosilicate (TEOS) and aqueous tetrapropylammonium hydroxide (TPAOH) solution at 95 degrees C. The silicate speciation was monitored by using dynamic light scattering (DLS), synchrotron small-angle X-ray scattering (SAXS), and quantitative liquid-state (29)Si NMR spectroscopy. The silicon atoms were present in dissolved oligomers, two discrete nanoparticle populations approximately 2 and 6 nm in size, and crystals. On the basis of new insight into the evolution of the different nanoparticle populations and of the silicate connectivity in the nanoparticles, a refined crystallization mechanism was derived. Upon combining the reagents, different types of nanoparticles (ca. 2 nm) are formed. A fraction of these nanoparticles with the least condensed silicate structure does not participate in the crystallization process. After completion of the crystallization, they represent the residual silicon atoms. Nanoparticles with a more condensed silicate network grow until approximately 6 nm and evolve into building blocks for nucleation and growth of the silicalite-1 crystals. The silicate network connectivity of nanoparticles suitable for nucleation and growth increasingly resembles that of the final zeolite. This new insight into the two classes of nanoparticles will be useful to tune the syntheses of silicalite-1 for maximum yield.

Synthesis and characterization of stable monodisperse silica nanoparticle sols for in vitro cytotoxicity testing.

For the investigation of the interaction of nanoparticles with biomolecules, cells, organs, and animal models there is a need for well-characterized nanoparticle suspensions. In this paper we report the preparation of monodisperse dense amorphous silica nanoparticles (SNP) suspended in physiological media that are sterile and sufficiently stable against aggregation. SNP sols with various particle sizes (2-335 nm) were prepared via base-catalyzed hydrolysis and polymerization of tetraethyl orthosilicate under sterile conditions using either ammonia (Stober process (1) ) or lysine catalyst (Lys-Sil process (2) ). The series was complemented with commercial silica sols (Ludox). Silica nanoparticle suspensions were purified by dialysis and dispersed without using any dispersing agent into cell culture media (Dulbecco's Modified Eagle's medium) containing antibiotics. Particle sizes were determined by dynamic light scattering. SNP morphology, surface area, and porosity were characterized using electron microscopy and nitrogen adsorption. The SNP sols in cell culture medium were stable for several days. The catalytic activity of the SNP in the conversion of hydrogen peroxide into hydroxyl radicals was investigated using electron paramagnetic resonance. The catalytic activity per square meter of exposed silica surface area was found to be independent of particle size and preparation method. Using this unique series of nanoparticle suspensions, the relationship between cytotoxicity and particle size was investigated using human endothelial and mouse monocyte-macrophage cells. The cytotoxicity of the SNP was strongly dependent on particle size and cell type. This unique methodology and the collection of well-characterized SNP will be useful for further in vitro studies exploring the physicochemical determinants of nanoparticle toxicity.

Synthesis of highly stable pure-silica thin-walled hexagonally ordered mesoporous material.

Hexagonally ordered mesoporous silica with a very narrow mesopore size distribution and exceptionally high stability paired with unusually thin pore walls was prepared using piperidine and cetyltrimethylammonium bromide.

Quantitative three-dimensional modeling of zeotile through discrete electron tomography.

Discrete electron tomography is a new approach for three-dimensional reconstruction of nanoscale objects. The technique exploits prior knowledge of the object to be reconstructed, which results in an improvement of the quality of the reconstructions. Through the combination of conventional transmission electron microscopy and discrete electron tomography with a model-based approach, quantitative structure determination becomes possible. In the present work, this approach is used to unravel the building scheme of Zeotile-4, a silica material with two levels of structural order. The layer sequence of slab-shaped building units could be identified. Successive layers were found to be related by a rotation of 120 degrees, resulting in a hexagonal space group. The Zeotile-4 material is a demonstration of the concept of successive structuring of silica at two levels. At the first level, the colloid chemical properties of Silicalite-1 precursors are exploited to create building units with a slablike geometry. At the second level, the slablike units are tiled using a triblock copolymer to serve as a mesoscale structuring agent.

Magnetic field assisted nanoparticle dispersion.

Magnetohydrodynamic nanoparticle dispersion is an energy efficient method to deaggregate nanoparticles, combining hydrodynamic forces of turbulent flow with Lorentz forces generated by a magnetic field.

Template-aluminosilicate structures at the early stages of zeolite ZSM-5 formation. A combined preparative, solid-state NMR, and computational study.

Species at three stages in the self-assembly of zeolite ZSM-5 have been studied with one- and two-dimensional magic-angle-spinning 13C, 27Al, 29Si, and 1H NMR spectroscopy and compared with the earlier proposed structures: (1) precursor species containing 33-36 T sites around a tetrapropylammonium (TPA) cation, (2) nanoslabs consisting of a flat 4 x 3 array of such precursors, and (3) the final TPA-ZSM-5 zeolite. Synthesis was carried out in D2O to suppress the water and silanol protons. Under such conditions, the effective Si-H and Al-H distances measured with 29Si-{1H} and 27Al-{1H} rotational echo double resonance (REDOR) reflect the interactions between TPA cations and the surrounding aluminosilica. The 29Si-{1H} REDOR curves for Q4-type silicon atoms at the three mentioned stages are closely similar, as well as the observed 27Al-1H REDOR curve for the precursor species compared to that for the TPA-ZSM-5. This indicates that in addition to externally attached TPA, there is also internal TPA already incorporated at an early stage into the aluminosilicate in a similar way as in the final zeolite, in accordance with the earlier proposed MFI self-assembly pathway (Kirschhock et al. Angew. Chem. Int. Ed. 2001, 40, 2637). However, the effective distances extracted from the initial REDOR curvatures are significantly (10-15%) larger than those computed for the model. Since there is no temperature effect, we tentatively assign this difference to a reduction of the 29Si-1H and 27Al-1H interactions by multispin decoherence effects or self-decoupling caused by proton spin diffusion. By assuming the computed model distances and fitting Anderson-Weiss curves to the observed REDOR data, we obtain similar "decoherence times" in the order of 0.1 ms. The observed 29Si-{1H} REDOR dephasing for the Q3 sites in the precursors is significantly faster than that for the Q4 sites. This is tentatively ascribed to a partial deuteron-proton back exchange at the silanol positions.

n-Alkane hydroconversion on Zeogrid and colloidal ZSM-5 assembled from aluminosilicate nanoslabs of MFI framework type.

n-Alkane hydroisomerisation and hydrocracking experiments reveal that ZSM-5 materials synthesized by self-assembly of nanoslabs show different molecular shape selectivity than ZSM-5 synthesized by hydrothermal methods.