Loïc Vidal

Template synthesis of a new type of ordered carbon structure from pitch

New ordered nanoporous carbon materials can be synthesized using pitch and mesoporous silica materials as the carbon precursor and template, respectively. In this case, the silica material (type MCM-48 and SBA-15) is impregnated with pitch and further carbonized. After removal of the silica by acid treatment, a graphitizable carbon material with an ordered micro-mesoporosity is recovered. The preparation route as well as the characteristics of the carbon materials are presented in this paper. It appears that the use of pitch as the carbon precursor presents some advantages compared to carbon obtained by other methods. Moreover, study of the thermal stability of the carbon shows that the structural regularity is preserved upon heat treatment at 1675 K.

Spatially controlled synthesis of silver nanoparticles and nanowires by photosensitized reduction

The present paper reports on the spatially controlled synthesis of silver nanoparticles (NPs) and silver nanowires by photosensitized reduction. In a first approach, direct photogeneration of silver NPs at the end of an optical fiber was carried out. Control of both size and density of silver NPs was possible by changing the photonic conditions. In a further development, a photochemically assisted procedure allowing silver to be deposited at the surface of a polymer microtip was implemented. Finally, polymer tips terminated by silver nanowires were fabricated by simultaneous photopolymerization and silver photoreduction. The silver NPs were characterized by UV-visible spectroscopy and scanning electron microscopy.

Exceptionally highly performing Na-ion battery anode using crystalline SnO2 nanoparticles confined in mesoporous carbon

Confined and unconfined SnO2 nanoparticles in the pores of mesoporous carbon were prepared and tested as anode materials vs. Na. Both composites present small crystalline SnO2 particles (∼3 nm) but different location and dispersion in the carbon matrix. When the particles are homogeneously distributed and confined in the carbon pores, an initial reversible capacity of 780 mA h g−1 is achieved with unprecedented capacity retention of 80 and 54% after 100 and 4000 cycles, respectively, at a high current rate (50 C, 1800 mA g−1). Unexpectedly, over two current rate variation cycles from 1 C to 500 C, the composite recovers 81% and 97%, respectively after returning from the 500 C to the 1 C rate. To our knowledge, no other material with such a long cycling life and superior performance in terms of capacity and rate capability has been reported so far for sodium ion batteries. HRTEM, XRD, N2 adsorption, XPS and galvanostatic cycling results suggest that confined SnO2 particles undergo an enhanced sodium alloying/dealloying process due to their special confinement inside the pores, which increases their conductivity, facilitates the diffusion of Na+ ions and buffers the large volumetric changes during charge/discharge. These high performances cannot be delivered when SnO2 is not confined and not well dispersed in the carbon pores. This work demonstrates that nano-confinement of anode species in carbon is a valuable concept affording the modification of the fundamental properties of guest species along with their electrochemical performances leading to highly stable and performing materials with a long life for Na-ion batteries.

Unprecedented Route to Ordered Polyaniline: Direct Synthesis of Highly Crystalline Fibrillar Films with Strong π-π Stacking Alignment.

Films of polyaniline (PANI) featuring about 80% crystallinity and characterised with strong π-π stacking alignment parallel to the film surface have been obtained directly after the original synthesis upon simple drying of the aqueous PANI suspension. A strong anisotropy in the growth of the nano-sized crystals produced during the synthesis results in the formation of micrometer-length fibrils perpendicular to the film surface in the course of water evaporation. The regular intercalation of water molecules between the PANI chains seems to be crucial for their ordering throughout the synthesis and film formation.

Catalyst-free soft-template synthesis of ordered mesoporous carbon tailored using phloroglucinol/glyoxylic acid environmentally friendly precursors

Carbon porous materials with a periodically ordered pore structure, controlled pore size and geometry and high thermal stability are synthesized using self-assembly of environmentally friendly phloroglucinol/glyoxylic acid precursors with an amphiphilic triblock copolymer template. Glyoxylic acid, a plant-derived compound, is used for the first time as a substituent of carcinogen formaldehyde usually employed in such a synthesis. Thanks to the double functionality, i.e., aldehyde and carboxylic acid, glyoxylic acid plays not only the role of a cross-linker for the formation of the resin but also the role of a catalyst by creation of H-bonding or specific reactions between the precursors. Hence, no extra catalyst such as strong acids (HCl) or bases (NaOH) is any longer required. Carbon films and powders were successfully prepared with high surface areas (up to 800 m2 g−1), high porous volume (up to 1 cm3 g−1), tunable pore size (0.6 nm to 7 nm) and various pore architectures (hexagonal, cubic, and ink-bottle) by tuning the precursor ratio and by applying different manufacturing engineering strategies. Insights on the synthesis mechanism of the phenolic resin and carbon mesostructures were obtained using several analysis techniques, i.e., nuclear magnetic resonance (13C NMR) and FTIR spectroscopy, temperature programmed desorption coupled with mass spectrometry (TPD-MS) and thermo-gravimetric analysis (TGA).

Chemical force titration of plasma polymer-modified PDMS substrates by using plasma polymer-modified AFM tips.

Plasma polymerization has gained increasing attention in surface functionalization. We use here chemical force titration to characterize PDMS (polydimethylsiloxane) substrates modified by maleic anhydride-pulsed plasma polymerization. The coating is hydrolyzed to promote the formation of dicarboxylic acid groups. To enhance the variation of the adhesion forces as a function of pH, we use AFM tips modified in the same way as the substrates. The pH-dependent adhesion measurements are performed at different KCl concentrations. The dicarboxylic nature of the maleic acid groups clearly emerges from the force titration curves. The surface pK(a) values (pK(a1) = 3.5 +/- 0.5 and pK(a2) = 9.5 +/- 0.5) of the dicarboxylic acids are evaluated from low electrolyte concentration solutions. The values are shifted toward higher pK(a) values when compared to maleic acid in solution. The first pK(a) appears in the titration force curve for low salt concentration as a peak. This peak changes to a sigmoidal shape at higher salt concentrations. The appearance of a peak is attributed to the formation of strong hydrogen bonds between the tip and the substrate as reported in the literature. The effect of the ionic strength on the force curves is explained by the condensation of counterions on the carboxylate groups. At high pH, the adhesion force almost vanishes. On the approach, at high pH, one first observes repulsion between the tip and the substrate, which varies exponentially with the tip/substrate distance. The decay length of this repulsion force is in good agreement with theoretical predictions of the Debye length, attesting to the electrostatic nature of the interactions. We also find that the replacement of monovalent cation K(+) by the divalent cation Ca(2+) leads to significant changes in the force titration curve at high pH where the dicarboxylic groups are fully ionized. We observe that the adhesion force no longer vanishes at high pH but even slightly increases with pH, an effect that is explained by Ca(2+) ions bridging between two carboxylate groups.

Self-Organized Poly(n-octadecylsilsesquioxane) Films via Sol–Gel Photopolymerization

We describe a novel solvent- and water-free sol-gel process for n-octadecyltriclorosilane (C(18)H(37)SiCl(3)) film catalyzed by photogenerated Brönsted acids. Driven by hydrophobic van der Waals interactions, a photoinduced self-assembly process occurs to afford a long-range ordered lamellar mesostructure, characterized by X-ray diffraction and transmission electron microscopy. Real-time Fourier transform IR spectroscopy was instrumental to probe the fast hydrolysis kinetics and assess the change of conformational behavior of the alkyl chains during UV irradiation. A unique combination of different solid-state NMR techniques ((29)Si, (13)C, (1)H) provided an insight into the supramolecular organization of this hybrid film.

Photoinitiating systems of polymerization and in situ incorporation of metal nanoparticles into polymer matrices upon exposure to visible light: push–pull malonate and malononitrile based dyes

Novel push–pull dyes containing a (substituted) hydrocarbon moiety and a malonate (or a malononitrile) moiety are proposed as photoinitiators for the ring opening polymerization of epoxides as well as the synthesis of interpenetrated polymer networks (IPNs) upon exposure to visible light (laser diode, halogen lamp, etc.). Excellent polymerization profiles are obtained. The role of the acceptor and donor moieties in these dyes towards their light absorption properties, the associated photochemical processes and their photoinitiating ability is investigated. A very efficient dye has been selected for the reduction of Ag+ and the in situ formation of Ag(0) nanoparticles in the synthesized IPNs.

Silver nanoparticles coated with thioxanthone derivative as hybrid photoinitiating systems for free radical polymerization.

A new type of photoinitiator for free radical polymerization was synthesized and characterized. 2-(11-Mercaptoundecyloxy)thioxanthone (1) was anchored at the surface of silver nanoparticles (NPs), and the interaction of plasmon field generated in the immediate vicinity of Ag NPs carrying the chromophores was evaluated. The optical features and structure of the silver-initiator nanoassemblies (Ag@1) were characterized by UV-vis and fluorescence spectroscopy, X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). TEM and XRD studies revealed the presence of ca. 5-6 nm diameter Ag NPs, and XPS also confirmed the successful anchorage of 1 at their periphery. The nanoassemblies Ag@1 were successfully used as macroinitiator for radical polymerization of acrylate monomers, triggered photochemically, to obtain Ag(0)-polyacrylate nanocomposite materials. The nanocomposite materials synthesized with the use of Ag@1 exhibit attractive possibilities for patterning the surface of thin films.

Preparation of γ-Al2O3 film by high temperature transformation of nanosized γ-AlOOH precursors

Mesoporous boehmite (γ-AlOOH) and gamma-alumina (γ-Al2O3) self-supported films were prepared by high temperature transformation of γ-AlOOH precursor fibers. A polymer, sodium polyacrylate, was used as a size/morphology controlling agent yielding to a stable colloidal suspension of boehmite ribbon-like fibers after a 168 h hydrothermal treatment at 160 °C. The slow evaporation of the solvent leads to γ-AlOOH film without any cracks and pinholes. The γ-Al2O3 film, obtained after calcination of the γ-AlOOH film, exhibit a high thermal stability up to 1000 °C and two distinct kinds of mesopores with average diameters of 20–30 A and 50 A. Structural and textural properties of these films confer them interesting properties for filtration processes.