Monodispersed hollow periodic mesoporous organosilica nanoparticles (HPMO-NPs) with a controlled core cavity and a periodic mesoporous organosilica (PMO) shell are successfully synthesized using a dual templating approach. The PMO shell synthesized by the sol–gel route exhibits a hybrid organic-inorganic framework based on phenylene bridges. The HPMO spherical nanoparticles with a diameter above 500 nm were characterized using a multiscale approach through TEM, BET, SAXS, and FT-IR. They are shown to offer an open periodic mesoporosity, a hollow cavity with a size tailored by thediameter of the core template, and finally, a high surface area (833 m 2 · g−1 ). In addition, we demonstrate that, through the same approach, the size of these hollow spherical nanoparticles can be tuned. Indeed, sub-50-nm hollow nanoparticles with mesoporous shells have also been obtained. The differences observed in the textural properties of these two sizes of hollow mesoporous nano-objects are discussed.

We report the existence in NaLa(SO 4 ) 2 ·H 2 O of a displacive phase transition under 200 K from the nonpolar P 3 1 21 to the polar P 3 1 space group.

Low-dimensional boron nitride (BN) chains were prepared in the one-dimensional pores of the siliceous zeolites theta-one (TON) and Mobil-twelve (MTW) by the infiltration, followed by the dehydrocoupling and pyrolysis of ammonia borane under high-pressure, high-temperature conditions. High-pressure X-ray diffraction in a diamond anvil cell and in a large-volume device was used to follow in situ these different steps in order to determine the optimal conditions for this process. Based on these results, millimeter-sized samples of BN/TON and BN/MTW were synthesized. Characteristic B–N stretching vibrations of low-dimensional BN were observed by infrared and Raman spectroscopies. The crystal structures were determined using a combination of X-ray diffraction and density functional theory with one and two one-dimensional zig-zag (BN)x chains per pore in BN/TON and BN/MTW, respectively. These 1-D BN chains potentially have interesting photoluminescence properties in the far ultraviolet region of the electromagnetic spectrum.

We report a complete investigation of the structural, electronic, vibrational, elastic and piezoelectric properties of the P2 1 2 1 2 1 orthorhombic phase in cadmium diiodate (δ-Cd(IO 3) 2) by combining experiments and first-principles based calculations. We revisited the nature of the electronic band gap and suggest an indirect band gap with a value of 4.6 eV. The infrared and Raman responses were measured and the different phonon modes assigned. To date, the δ-Cd(IO 3) 2 piezoelectric response remains unknown. We reported the different mechanisms involved in its piezoelectric response from the density functional perturbation theory. The highest value of the piezoelectric-stress and piezoelectric-strain constants in the zero Kelvin limit is predicted for e 41 =-0.27 C/m 2 and d 41 =-10.32 pC/N. These sizable values associated with the thermal stability (no phase transition up to the thermal decomposition at 550°C) and a relative large electronic band gap make δ-Cd(IO 3) 2 a potential candidate for piezoelectric applications.

Metal oxide aluminosilicate and aluminogermanate nanotubes, called imogolite nanotubes, are custom made nanotubes with controlled diameter, morphology and organization. These nanotubes undergo major structural changes at high temperatures. Here, we report a complete analysis of the structural transformation of single and double-walled aluminogermanate nanotubes, organized or not in bundles, up to 800 • C. Complementary X-ray scattering and spectroscopy experiments were performed. The evolution of both Al and Ge atoms coordination during the transformation process was studied in-situ. Quantitative analysis of X-ray absorption spectra reveals that the dehydroxylation of nanotubes leads to intermediate stages of 'metaimogolite', which differ in the coordination of the aluminium atoms. A mechanism explaining the major structural reorganization is proposed based on atomic jump processes.

We report a detailed experimental investigation of the influence of the formation of nano-crystallites on the vibrational, electronic and optical properties of CrSi₂ thin films. Both amorphous and nanostructured thin films were investigated by means of electrical resistivity, Hall effect measurements as well as Raman and infrared spectroscopies. We show that both types of films exhibit a semiconducting-like behavior, with the notable difference that the high defect concentrations in amorphous films act as hole donors, modifying the electronic band structure and optical constants. The effect of the film thickness on electrical properties is well captured by the Fuchs-Sondheimer model indicating a decrease in the charge carrier mean free path, likely due to the formation of amorphous/nano-crystallite interfaces that contribute to strongly scatter the charge carriers. Raman spectroscopy performed on nano-crystallized thin films evidences the presence of a Raman-active mode at 229 cm^-1 and confirms DFT calculations predicting a mode at 248 cm^-1, the observation of which had remained elusive so far in polycrystalline CrSi₂. Measurements of the refractive index and dielectric constants of amorphous thin films show a very high refractive index in the mid-IR range. Our results illustrate how the controlled growth of nano-crystallites can be used to tailor the electronic, vibrational and optical properties of amorphous thin films.