Gas Porosimetry by Gas Adsorption as an Efficient Tool for the Assessment of the Shaping Effect in Commercial Zeolites.

A set of three commercial zeolites (13X, 5A, and 4A) of two distinct shapes have been characterized: (i) pure zeolite powders and (ii) extruded spherical beads composed of pure zeolite powders and an unknown amount of binder used during their preparation process. The coupling of gas porosimetry experiments using argon at 87 K and CO2 at 273 K allowed determining both the amount of the binder and its effect on adsorption properties. It was evidenced that the beads contain approximately 25 wt% of binder. Moreover, from CO2 adsorption experiments at 273 K, it could be inferred that the binder present in both 13X and 5A zeolites does not interact with the probe molecule. However, for the 4A zeolite, pore filling pressures were shifted and strong interaction with CO2 was observed leading to irreversible adsorption of the probe. These results have been compared to XRD, IR spectroscopy, and ICP-AES analysis. The effect of the binder in shaped zeolite bodies can thus have a crucial impact on applications in adsorption and catalysis.

Orientation measurements of clay minerals by polarized attenuated total reflection infrared spectroscopy.

The orientation and organization of molecular guests within the interlayer of clay minerals control the reactivity and performance of tailored organo-clay materials. Such a detailed investigation of hybrid structure on the molecular scale is usually provided by computational methods with limited experimental validation. In this study, polarized attenuated total reflection infrared spectroscopy was used to extract quantitative orientation measurements of montmorillonite particles. The validity of the evanescent electric field amplitude calculations necessary to derive the order parameter was critically evaluated to propose a methodology for determining the orientation of the normal to the clay layer relative to a reference axis, enabling comparison with the results obtained from X-ray scattering experiments and molecular dynamic simulations. Subsequently, the orientation of the interlayer water dipole and surface hydroxyls with respect to the normal of the clay layer was experimentally determined, showing good agreement with molecular simulations. This methodology may provide quantitative insights into the molecular-level description of interfacial processes between organic molecules and clay minerals.

Insights into the Rheological Behavior of Aqueous Dispersions of Synthetic Saponite: Effects of Saponite Composition and Sodium Polyacrylate.

Synthetic saponite (Sap) easily delaminates in water to form a transparent sol and hydrogel with excellent rheological performance and is thus widely used in paints, cosmetics, and nanomaterials. The thixotropic property of Sap hydrogels is heavily dependent on the nature of Sap and the external electrolyte and polyelectrolyte; yet, details on the relationship between rheological behaviors of saponite hydrogels and Sap composition and polyelectrolyte remain unclear. In this work, thixotropic rheological behaviors of a series of synthetic Sap hydrogels, with and without added sodium polyacrylate polyelectrolyte (NaPA), were investigated. The Sap samples, with a Si/Al molar ratio from 5 to 25, were successfully synthesized using hydrothermal methods and characterized by powder X-ray diffraction, Fourier transform infrared spectroscopy, and scanning electron microscopy. The rheological performances of aqueous Sap dispersions and particle sizes and ζ-potentials of Sap were measured. The results showed that the crystallinity of the Sap increased with an increasing Si/Al molar ratio. All Sap samples, with the exception of the Sap with a Si/Al molar ratio of 5, dispersed well in water (3 wt %) to form hydrogels. The rheological behaviors of the hydrogels were related to the chemical composition and the layer charge of the Sap. The Sap with a Si/Al molar ratio of 25 had higher viscosity due to improved delamination. The addition of the NaPA, an anionic polyelectrolyte, into the hydrogels decreased the viscosity and altered the thixotropic properties such that the hydrogel becomes a sol. The addition of NaPA facilitated the dispersion and delamination of Sap, because under the electric field of negatively charged Sap particles in the hydrogel, the anionic NaPA was instantaneously polarized and thereby entered the hydration layer of the Sap particles.

Effect of the morphology of synthetic kaolinites on their sorption properties.

Natural kaolinites often have a permanent charge due to mineralogical impurities preventing to link directly the morphology of the kaolinite particle to a selectivity coefficient between two cations for edge sites. In this study, kaolinites with no permanent charge were hydrothermally synthesized under different physicochemical conditions to obtain various morphologies (hexagon-shaped, more or less anisotropic). Na(+) and H(+) were chosen as the sorbed cations due to their ubiquitous presence in natural waters. For synthetic kaolinites for which no swelling layer was detected, an experimental sorption isotherm between Na(+) and H(+) was obtained. Data were interpreted using a surface complexation model, containing no electrostatic term, by considering the specific surfaces of lateral sites and sorption site density identified by crystallography for the different faces presented in the samples ((010), (110), (1-10)). Selectivity coefficients between Na(+) and H(+) for all lateral sites characterizing a given morphology were calculated and validated in the [4-10] pH range, corresponding to the pH range for which dissolution can be considered negligible. The results showed that the Na(+)/H(+) selectivity coefficient depends strongly on the particle morphology and that the sorption properties of kaolinites cannot be obtained with good accuracy without a fine knowledge of the morphology of the particles.

Heterogeneous photo-Fenton decolorization of Orange II over Al-pillared Fe-smectite: response surface approach, degradation pathway, and toxicity evaluation.

A ferric smectite clay material was synthesized and further intercalated with Al2O3 pillars for the first time with the aim of evaluating its ability to be used as heterogeneous catalyst for the photo-Fenton decolorization of azo dye Orange II. UV irradiation was found to enhance the activity of the catalyst in the heterogeneous photo-Fenton process. Catalyst loading of 0.5g/L and hydrogen peroxide concentration of 13.5mM yielded a remarkable color removal, accompanied by excellent catalyst stability. The decolorization of Orange II followed the pseudo-first-order kinetics for initial dye concentrations from 20 to 160mg/L. The central composite design (CCD) based on the response surface methodology (RSM) was applied to evaluate the effects of several operating parameters, namely initial pH, catalyst loading and hydrogen peroxide concentration, on the decolorization efficiency. The RSM model was derived and the response surface plots were developed based on the results. Moreover, the main intermediate products were separated and identified using gas chromatography-mass spectrometry (GC-MS) and a possible degradation pathway was proposed accordingly. The acute toxicity experiments illustrated that the Daphniamagna immobilization rate continuously decreased during 150min reaction, indicating that the effluent was suitable for sequential biological treatment.

Nanosized transition metals in controlled environments of phyllosilicate-mesoporous silica composites as highly thermostable and active catalysts.

Stabilization of transition metals in nano-phyllosilicate phases generated by digestion of mesoporous silica is reported as an efficient route for the formation of highly dispersed metallic nanoparticles with outstanding catalytic activity.

The Fe-rich clay microsystems in basalt-komatiite lavas: importance of Fe-smectites for pre-biotic molecule catalysis during the Hadean eon.

During the Hadean to early Archean period (4.5-3.5 Ga), the surface of the Earth's crust was predominantly composed of basalt and komatiite lavas. The conditions imposed by the chemical composition of these rocks favoured the crystallization of Fe-Mg clays rather than that of Al-rich ones (montmorillonite). Fe-Mg clays were formed inside chemical microsystems through sea weathering or hydrothermal alteration, and for the most part, through post-magmatic processes. Indeed, at the end of the cooling stage, Fe-Mg clays precipitated directly from the residual liquid which concentrated in the voids remaining in the crystal framework of the mafic-ultramafic lavas. Nontronite-celadonite and chlorite-saponite covered all the solid surfaces (crystals, glass) and are associated with tiny pyroxene and apatite crystals forming the so-called "mesostasis". The mesostasis was scattered in the lava body as micro-settings tens of micrometres wide. Thus, every square metre of basalt or komatiite rocks was punctuated by myriads of clay-rich patches, each of them potentially behaving as a single chemical reactor which could concentrate the organics diluted in the ocean water. Considering the high catalytic potentiality of clays, and particularly those of the Fe-rich ones (electron exchangers), it is probable that large parts of the surface of the young Earth participated in the synthesis of prebiotic molecules during the Hadean to early Archean period through innumerable clay-rich micro-settings in the massive parts and the altered surfaces of komatiite and basaltic lavas. This leads us to suggest that Fe,Mg-clays should be preferred to Al-rich ones (montmorillonite) to conduct experiments for the synthesis and the polymerisation of prebiotic molecules.

Key scientific questions and key investigations from the first international conference on Martian phyllosilicates.

Minerals and their occurrences can tell us about the chemistry, pressure, and temperatures of past environments on Mars and thus allow inferences about the potential for habitability. Thanks to recent space exploration, a new vision is emerging wherein Mars hosted environmental conditions of potential astrobiological relevance. This epoch is identified by the presence of phyllosilicate-bearing deposits, which are generally contained in very ancient basement rocks. In October 2008, over 100 planetary scientists representing 11 countries met in Paris to assess and discuss the relevance of martian phyllosilicates. The conference was structured to promote the discussion and debate of key scientific questions and key essential investigations. The purpose of this report is to document the current state of knowledge related to martian phyllosilicates and to ascertain which questions remain to be addressed: What are the basic characteristics of the phyllosilicate minerals on Mars? What are the genetic mechanisms by which phyllosilicate minerals have formed on Mars? What is the relationship between the phyllosilicate minerals observed in martian meteorites and those detected from orbit? What are the implications of phyllosilicate-bearing rocks for the development of prebiotic chemistry and the preservation of biosignatures? The most promising investigations to address these questions are presented.

Assessing the redox reactivity of structural iron in smectites using nitroaromatic compounds as kinetic probes.

Structural Fe(II) in clay minerals is an important source of electron equivalents for the reductive transformation of contaminants in anoxic environments. We investigated which factors control the reactivity of Fe(II) in smectites including total Fe content Fe(II)/total Fe ratio, and excess negative charge localization using 10 nitroaromatic compounds (NACs) as reactive probe molecules. Based on evidence from this work and previous spectroscopic studies on Fe redox reactions in iron-rich smectites, we propose a kinetic model for quantifying the reactivity, abundance, and interconversion rates of two distinct Fe(II) sites in the minerals' octahedral sheet. Excellent agreement between observed biphasic NAC reduction kinetics and model fits points toward existence of two types of Fe(II) sites exhibiting reactivities that differ by 3 orders of magnitude in iron-rich ferruginous smectite (SWa-1) and Olberg montmorillonite. Low structural Fe content, as found in Wyoming montmorillonite (SWy-2), impedes the formation of highly reactive Fe sites and results in pseudo-first order kinetics of NAC reduction that originate from the presence of a single type of Fe(II) species of even lower reactivity. Similar correlations of one-electron reduction potentials of the NACs vs their second order reduction rate constants for all smectite suspensions suggest that contaminant-Fe(II) interactions were identical in all smectite minerals.