Some countries with rich textile industries are nowadays facing water quality issues as a consequence of impacting dye pollution. In addition to their inherent toxicity, dyes induce modification in water acidity or salinity which has harmful consequences on the photosynthesis of aquatic plants. As dye are hardly biodegradable, water treatment is necessary to get ride of them [1], and adsorption treatment appears as a good candidate with efficient low-cost adsorbents, such as clays [2]. As a matter of fact, lamellar materials are widely used for sorbtion of ions and molecules harmful for health and environment. In order to gain in efficiency in the use of such materials, it is essential to get a deeper understanding of the retention mechanisms at the interface solid/liquid. In this work, anionic clays, namely layered double hydroxides (LDH) have been chosen as model compounds in order to study sorption mechanism. The presence of charged layer induce strong anionic exchange capacity in these materials, moreover their composition and structual parameters are easily controled through mastered synthesis process [3]. This study work has been focused on the the mechanisms that can lead to the capture of polluting molecules. Several model dyes have been chosen (MethylOrange - MO, Carmen Indigo - CI et Orange G - OG) for their charge, symmetry and hydrophobicity. Parameters such as the solution concentration and the activity of the solvant, playing with the nature of ions, have also been explored.The work presented here rely on vibrational spectroscopies (Infrared and Raman spectroscopies) sensitive to the intermolecular interaction of the dye with its environment particularly at the interface solid/dye. In parallel, X-Ray Diffraction probes the structural modification in the clay during sorption.The experimental results interpreted though the help of simulations (Monte-Carlo, DFT), lead a fine description of ions sorption at the interfaces with these models lamellar materials.

Bridged silsesquioxane nanomaterials exhibit original mechanical properties thanks to the association of non-covalent and covalent interactions. Thanks to in situ high pressure spectroscopic studies, achieved in diamond anvil cells, the mechanical behavior of these materials was followed as a function of pressure. Figure 1: Schematic representation of bottom-up structuring in organic-inorganic hybrid silica through self-assembling process Vibrational studies on organic models coupled to ab-initio simulations show that H bond response to pressure is strengthening. In hybrid materials the H bond shows its ability to absorb the mechanical constrains by the modulation of H bond interactions. We thus show that the rigidity yielded by the inorganic polymerization is counterbalanced by the presence of the intermolecular H bond network. The hybrid materials have therefore a reversible behavior, thanks to h bonds behaving as molecular springs. For higher pressure ranges inorganic network start to be strongly impacted in a dominant way so that an irreversible loss of long range order within the organic network is observed.In a second time, the influence of the nature of the organic substructure (thiourea versus urea link, aryl versus aliphatic core) on this spring behavior is discussed.

Opto-electronic properties of single-walled carbon nanotubes can be significantly modified by chromophore confinement into their hollow core. This presentation deals with quaterthiophene derivatives encapsulated into nanotubes displaying different diameter distributions. We show that the supramolecular organizations of the confined chromophores depend on the nanocontainer size. The Raman radial breathing mode frequency is monitored by both the number of confined molecules into a nanotube section and the competition between dye/dye and dye/tube wall interactions. The confinement properties lead also to an exaltation of the infrared absorption response1 in single-walled carbon nanotubes from dye molecule interactions due to a symmetry breaking, allowing us, thanks to the complementarity of DFT calculations and experimental IR investigations to study interactions between both subsystems. Significant electron transfer from the confined molecules to the nanotubes is also reported from Raman investigations. This charge transfer leads to an important enhancement of the photoluminescence intensity by a factor of nearly five depending on the tube diameter. In addition, close to the molecule resonance, the magnitude of the Raman G-band shifts is modified and the intensity loss is amplified, indicating a photo-induced electron transfer. Results are discussed in the frame of electron-phonon coupling. Thus, confinement species into nanotubes allow moving the Fermi level and consequently to monitor their opto-electronic properties.

The control of structuring and morphology in hybrid solids is a key parameter for the design of functional materials. In particular, it has been shown that structure and morphology could be tuned through sol gel synthesis conditions in bridged silsesquioxanes (BS). As a matter of fact, during sol-gel process, the competition between self-assembing through non covalent interactions between the organic sub-structures and condensation of the inorganic siliceous sub-structure can lead to the formation of crystalline compounds or amorphous materials.In order to go further with the understanding of the control of the nanostructuring in bridged silsequioxane, we designed the organic moieties of the precursors with either 2 symetrical through hydrogen bond and the strength of these hydrogen bonds is studied through vibrational spectroscopies in-situ at low temperature or at high pressure. The results are analyzed and discussed in terms of H bond strength and geometric factors.In the second part of this talk, we will focus on the influence of the central subunit lying between the two urea/thiourea groups_either a long flexible alkyl chain or rigid phenyl group_ on the self-assembling properties through H bonds.

Bridged silsesquioxane nanomaterials exhibit original mechanical properties thanks to the association of non-covalent and covalent interactions. Thanks to in situ high pressure spectroscopic studies, achieved in diamond anvil cells, the mechanical behavior of these materials was followed as a function of pressure. Vibrational studies coupled to ab-initio simulations show that mechanical constrains are absorbed by the modulation of H bond interactions. We thus show that the rigidity yielded by the inorganic polymerization is counterbalanced by the presence of the intermolecular H bond network. In a large range of pressures, these hybrid materials have a reversible behavior, and thus behave as molecular springs. In a second time, we demonstrate that the pressure behavior of these molecular spring is sensitive to the conformation of H bonds (cyclic versus linear) and to the constraints imposed the covalent inorganic network.

alpha-Quartz-type gallium phosphate and representative compositions in the AlPO4-GaPO4 solid solution were studied by x-ray powder diffraction and absorption spectroscopy, Raman scattering, and by first-principles calculations up to pressures of close to 30 GPa. A phase transition to a metastable orthorhombic high-pressure phase along with some of the stable orthorhombic Cmcm CrVO4-type material is found to occur beginning at 9 GPa at 320 degrees C in GaPO4. In the case of the AlPO4-GaPO4 solid solution at room temperature, only the metastable orthorhombic phase was obtained above 10 GPa. The possible crystal structures of the high-pressure forms of GaPO4 were predicted from first-principles calculations and the evolutionary algorithm USPEX. A predicted orthorhombic structure with a Pmn2(1) space group with the gallium in sixfold and phosphorus in fourfold coordination was found to be in the best agreement with the combined experimental data from x-ray diffraction and absorption and Raman spectroscopy. This method is found to very powerful to better understand competition between different phase transition pathways at high pressure.