One-pot synthesis of silica monoliths with hierarchically porous structure

Poly(furfuryl alcohol) (PFA) and block copolymer Pluronic F127 were used as pore templates to create mechanically robust silica monoliths with a hierarchical and interconnected macro?mesoporous network in an easy, reproducible bimodal scale templating process. Control over the morphology was obtained by varying the reactant ratios. Phase separation on the submicrometer scale occurred when furfuryl alcohol was cationically polymerized and therefore became immiscible with the solvent and the silica precursor. Upon a subsequent sol?gel reaction, a silica-F127 matrix formed around the PFA spheres, leading to macropore structures with mesoporous walls. Surface areas of the final structures ranged from 500 to 989 m2/g and a maximum pore volume of 4.5 mL/g was achieved. Under mildly acidic conditions, micelle-templated mesopores resulted. Interconnected macropores could be obtained by increasing the pH or the block copolymer concentration. The formation mechanism and the relationship between PFA, Pluronic F127 and acidity are discussed in detail.Fil: Drisko, Glenna L.. University of Melbourne; AustraliaFil: Zelcer, Andrés. Universidad Nacional de San Martín. Escuela de Ciencia y Tecnología; Argentina. Comisión Nacional de Energía Atómica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Caruso, Rachel A.. University of Melbourne; AustraliaFil: Soler Illia, Galo Juan de Avila Arturo. Comisión Nacional de Energía Atómica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentin

One-pot synthesis of hierarchically structured ceramic monoliths with adjustable porosity

Hierarchically porous oxides are used in a variety of applications within the energy sector (e.g., fuel cells, batteries), biology (e.g., scaffolds, biocatalysis), separations, and catalysis. This article describes a reproducible one-step method for the preparation of metal oxides with controllable hierarchical pore architectures. The preparation is demonstrated for a wide range of materials, specifically silica, titania, zirconia, aluminum titanium oxide, titanium zirconium oxide, and yttrium zirconium oxide monoliths. The samples were prepared by exploiting the polymerization and phase separation of furfuryl alcohol to produce a colloidal dispersion of poly(furfuryl alcohol) particles. The gelation in the sol-gel process occurred after the in situ formation of the template. The removal of the polymer template led to the formation of macropores, whereas inclusion of an amphiphilic block copolymer (Pluronic F127) assisted mesopore formation, either by templating or by stabilizing the inorganic building blocks. The macropore and mesopore morphology could be altered by varying the synthesis conditions. This control over the pore structure was demonstrated in the silica, titania, and titanium zirconium oxide materials.Fil: Drisko, Glenna L.. University of Melbourne; AustraliaFil: Zelcer, Andrés. Comisión Nacional de Energía Atómica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Luca, Vittorio. Comisión Nacional de Energía Atómica; ArgentinaFil: Caruso, Rachel A.. University of Melbourne; AustraliaFil: Soler Illia, Galo Juan de Avila Arturo. Comisión Nacional de Energía Atómica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentin

Synthesis and photocatalytic activity of titania monoliths prepared with controlled macro- and mesopore structure

Herein, we report a one-pot synthesis of crack-free titania monoliths with hierarchical macro-mesoporosity and crystalline anatase walls. Bimodal macroporosity is created through the polymer-induced phase separation of poly(furfuryl alcohol). The cationic polymerization of furfuryl alcohol is performed in situ and subsequently the polymer becomes immiscible with the aqueous phase, which includes titanic acid. Addition of template, Pluronic F127, increases the mesopore volume and diameter of the resulting titania, as the poly(ethylene glycol) block interacts with the titania precursor, leading to assisted assembly of the metal oxide framework. The hydrophobic poly(propylene glycol) micelle core could itself be swollen with monomeric and oligomeric furfuryl alcohol, allowing for mesopores as large as 18 nm. Variations in synthesis parameters affect porosity; for instance furfuryl alcohol content changes the size and texture of the macropores, water content changes the grain size of the titania and Pluronic F127 content changes the size and volume of the mesopore. Morphological manipulation improves the photocatalytic degradation of methylene blue. Light can penetrate several millimeters into the porous monolith, giving these materials possible application in commercial devices.Fil: Drisko, Glenna L.. University of Melbourne; AustraliaFil: Zelcer, Andrés. Comisión Nacional de Energía Atómica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de San Martín. Escuela de Ciencia y Tecnología; ArgentinaFil: Wang, Xingdong. Commonwealth Scientific And Industrial Research Organization; AustraliaFil: Caruso, Rachel A.. School Of Chemistry; Australia. Commonwealth Scientific And Industrial Research Organization; AustraliaFil: Soler Illia, Galo Juan de Avila Arturo. Comisión Nacional de Energía Atómica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentin

Mesoscopically structured nanocrystalline metal oxide thin films

International audienceThis review describes the main successful strategies that are used to grow mesostructured nanocrystalline metal oxide and SiO2 films via deposition of sol-gel derived solutions. In addition to the typical physicochemical forces to be considered during crystallization, mesoporous thin films are also affected by the substrate-film relationship and the mesostructure. The substrate can influence the crystallization temperature and the obtained crystallographic orientation due to the interfacial energies and the lattice mismatch. The mesostructure can influence the crystallite orientation, and affects nucleation and growth behavior due to the wall thickness and pore curvature. Three main methods are presented and discussed: templated mesoporosity followed by thermally induced crystallization, mesostructuration of already crystallized metal oxide nanobuilding units and substrate-directed crystallization with an emphasis on very recent results concerning epitaxially grown piezoelectric structured a-quartz films via crystallization of amorphous structured SiO2 thin films

Fabrication of complex metasurfaces to control the visual appearance

International audienc

Disordered metasurfaces to shape visual appearance

International audienceMetasurfaces hold great potential to become a major actor in the next generation of coating materials with innovative functionalities and striking visual appearances. This talk presents unconventional visual effects achieved with disordered metasurfaces and provides important hints to the capabilities of metasurfaces to shape reflected light spectrally and angularly

Imaging Radial Distribution Functions of Complex Particles by Relayed Dynamic Nuclear Polarization

The physical properties of many modern multi-component materials are determined by their internal microstructure. Tools capable of characterizing complex nanoscale architectures in composite materials are, therefore, essential to design materials with targeted properties. Depending on the morphology and the composition, structures may be measured by laser diffraction, scattering methods, or by electron microscopy. However, it can be difficult to obtain contrast in materials where all the components are organic, which is typically the case for formulated pharmaceuticals, or multi-domain polymers. In nuclear magnetic resonance (NMR) spectroscopy, chemical shifts allow a clear distinction between organic components and can in principle provide the required chemical contrast. Here, we introduce a method to obtain radial images of the internal structure of multi-component particles from NMR measurements of the relay of nuclear hyperpolarization obtained from dynamic nuclear polarization. The method is demonstrated on two samples of hybrid core–shell particles composed of a core of polystyrene with a shell of mesostructured silica filled with the templating agent CTAB and is shown to yield accurate images of the core–shell structures with a nanometer resolution

Air-stable anisotropic monocrystalline nickel nanowires characterized using electron holography

Nickel is capable of discharging electric and magnetic shocks in aerospace materials thanks to its conductivity and magnetism. Nickel nanowires are especially desirable for such an application as electronic percolation can be achieved without significantly increasing the weight of the composite material. In this work, single-crystal nickel nanowires possessing a homogeneous magnetic field are produced via a metal–organic precursor decomposition synthesis in solution. The nickel wires are 20 nm in width and 1–2 μm in length. The high anisotropy is attained through a combination of preferential crystal growth in the ⟨100⟩ direction and surfactant templating using hexadecylamine and stearic acid. The organic template ligands protect the nickel from oxidation, even after months of exposure to ambient conditions. These materials were studied using electron holography to characterize their magnetic properties. These thin nanowires display homogeneous ferromagnetism with a magnetic saturation (517 ± 80 emu cm–3), which is nearly equivalent to that of bulk nickel (557 emu cm–3). Nickel nanowires were incorporated into carbon composite test pieces and were shown to dramatically improve the electric discharge properties of the composite material.Initiative d'excellence de l'Université de Bordeau

Water-Induced Phase Separation Forming Macrostructured Epitaxial Quartz Films on Silicon

International audienceQuartz has been widely used as a bulk material in optics, the microelectronic industry, and sensors. The nanostructuring and direct integration of oriented quartz crystals onto a semiconductor platform has proven to be challenging. However, here, a new approach is presented to integrate epitaxial quartz films with macroperforations within the range of 500 nm and 1 mu m using chemical solution deposition. This method constitutes an appealing approach to develop piezoelectric mass sensors with enhanced resonance frequencies due to the thickness reduction. Perforated quartz films on (100)-silicon are prepared from amorphous silica films deposited via dip-coating and doped with metal cations that catalyze quartz crystallization. The metal cations are also active in the formation of the macroperforations, which arise due to a phase separation mechanism. Cationic surfactant-anion-metal cation assemblies stabilize droplets of water, creating an indentation in the hydrophilic silica matrix which remains after solvent evaporation. Many cations induce phase separation, including Li+, Na+, Sr2+, Mn2+, Fe2+/Fe3+, Ca2+, Ce3+ and La3+ but only the Sr2+ and Ca2+ cations in this series induce the epitaxial growth of alpha-quartz films under the conditions studied. The combination of sol-gel chemistry and epitaxial growth opens new opportunities for the integration of patterned quartz on silicon