Marc Reinholdt

Synthesis and characterization of montmorillonite-type phyllosilicates in a fluoride medium

Abstract The fluorine route is thoroughly investigated for the hydrothermal synthesis of montmorillonite in the Na2O-MgO-Al2O3-SiO2-H2O system. Using the optimal conditions suggested by Reinholdt et al. (2001) for the crystallization of pure montmorillonites with the formula Na2x(Al2(1−x)Mg2x □)Si4O10(OH)2, several parameters (x, Mg content, duration of crystallization, F/Si atomic ratio, pH, nature of counterbalance cation) are varied independently from their ideal values. The products are analysed by various techniques (X-ray diffraction, thermogravimetric analysis-differential thermal analysis, 29Si, 27Al and 19F magic angle spinning-nuclear magnetic resonance). It appears that a pure montmorillonite can only be obtained within a narrow x range (0.10 ≤x ≤ 0.20). The presence of F in the starting hydrogel and the crystallization time also have significant effects on the purity of the final products. It is shown that a small amount of fluorine is needed for the crystallization of pure montmorillonite phyllosilicates.

Proton Exchange Membranes for Application in Fuel Cells: Grafted Silica/SPEEK Nanocomposite Elaboration and Characterization

Hydrogen technologies and especially fuel cells are key components in the battle to find alternate sources of energy to the highly polluting and economically constraining fossil fuels in an aim to preserve the environment. The present paper shows the synthesis of surface functionalized silica nanoparticles, which are used to prepare grafted silica/SPEEK nanocomposite membranes. The nanoparticles are grafted either with hexadecylsilyl or aminopropyldimethylsilyl moieties or both. The synthesized particles are analyzed using XRD, NMR, TEM, and DLS to collect information on the nature of the particles and the functional groups, on the particle sizes, and on the hydrophilic/hydrophobic character. The composite membranes prepared using the synthesized particles and two SPEEK polymers with sulfonation degrees of 69.4% and 85.0% are characterized for their proton conductivity and water uptake properties. The corresponding curves are very similar for the composites prepared with both polymers and the nanoparticles bearing the two functional groups. The composites prepared with the nanoparticles bearing solely the aminopropyldimethylsilyl moiety exhibit lower conductivity and water uptake, possibly due to higher interaction of the polymer sulfonic acid sites with the amine groups. The composites prepared with the nanoparticles bearing solely the hexadecylsilyl moiety were not further investigated because of very high particles segregation. A study of the proton conductivity as a function of temperature was performed on selected membranes and showed that nanocomposites made with nanoparticles bearing both functional moieties have a higher conductivity at higher temperatures.

Boronate ligands in materials: Determining their local environment by using a combination of IR/solid-state NMR spectroscopies and DFT calculations

Boronic acids (R-B(OH)(2)) are a family of molecules that have found a large number of applications in materials science. In contrast, boronate anions (R-B(OH)(3)(-)) have hardly been used so far for the preparation of novel materials. Here, a new crystalline phase involving a boronate ligand is described, Ca[C(4)H(9)-B(OH)(3)](2), which is then used as a basis for the establishment of the spectroscopic signatures of boronates in the solid state. The phase was characterized by IR and multinuclear solid-state NMR spectroscopy ((1)H, (13)C, (11)B and (43)Ca), and then modeled by periodic DFT calculations. Anharmonic OH vibration frequencies were calculated as well as NMR parameters (by using the Gauge Including Projector Augmented Wave--GIPAW--method). These data allow relationships between the geometry around the OH groups in boronates and the IR and (1)H NMR spectroscopic data to be established, which will be key to the future interpretation of the spectra of more complex organic-inorganic materials containing boronate building blocks.

Cross-linked sulfonated poly(ether ether ketone) by using diamino-organosilicon for proton exchange fuel cells.

Fuel cells are at the battlefront to find alternate sources of energy to the highly polluting, economically and environmentally constraining fossil fuels. This work uses an organosilicon molecule presenting two amine functions, bis(3-aminopropyl)-tetramethyldisiloxane (APTMDS) with the aim of preparing cross-linked sulfonated poly(ether ether ketone) (SPEEK) based membranes. The hybrid membranes obtained at varying APTMDS loadings are characterized for their acid, proton conductivity, water uptake, and swelling properties. APTMDS may be considered as an extreme case of silica nanoparticle and is therefore most advantageously distributed within the polymeric matrix. The two amine groups can interact, via electrostatic interactions, with the sulfonic acid groups of SPEEK, resulting in a double anchoring of the molecule. The addition of a small amount of APTMDS is enhancing the mechanical and hydrolytic properties of the membranes and allows some unfolding of the polymer chains, rendering some acid sites accessible to water molecules and thus available for proton transport.

Plasma Membranes Modified by Plasma Treatment or Deposition as Solid Electrolytes for Potential Application in Solid Alkaline Fuel Cells

In the highly competitive market of fuel cells, solid alkaline fuel cells using liquid fuel (such as cheap, non-toxic and non-valorized glycerol) and not requiring noble metal as catalyst seem quite promising. One of the main hurdles for emergence of such a technology is the development of a hydroxide-conducting membrane characterized by both high conductivity and low fuel permeability. Plasma treatments can enable to positively tune the main fuel cell membrane requirements. In this work, commercial ADP-Morgane® fluorinated polymer membranes and a new brand of cross-linked poly(aryl-ether) polymer membranes, named AMELI-32®, both containing quaternary ammonium functionalities, have been modified by argon plasma treatment or triallylamine-based plasma deposit. Under the concomitant etching/cross-linking/oxidation effects inherent to the plasma modification, transport properties (ionic exchange capacity, water uptake, ionic conductivity and fuel retention) of membranes have been improved. Consequently, using plasma modified ADP-Morgane® membrane as electrolyte in a solid alkaline fuel cell operating with glycerol as fuel has allowed increasing the maximum power density by a factor 3 when compared to the untreated membrane.