The catalytic activity for the production of biodiesel with three morphologically different nanocrystalline MgO materials prepared using simple, green and reproducible methods was investigated. The nanocrystalline samples studied were MgO(111) nanosheets (MgO (I)), conventionally prepared MgO (MgO (II)) and aerogel prepared MgO (MgO (III)). The methods to produce the catalysts included: (a) 4-methoxy-benzyl alcohol templated sol-gel process followed by supercritical drying and calcination in air at 773 K (MgO (I)), (b) from a commercial MgO that was boiled in water, followed by drying at 393 K, and dehydration under vacuum at 773 K (MgO (II)), and (c) via hydrolysis of Mg(OCH 3 ) 2 in a methanol-toluene mixture, followed by supercritical solvent removal with the formation of a Mg(OH) 2 aerogel that was dehydrated under vacuum at 773 K (MgO (III)). These catalysts were characterized by TEM, DRIFT, and DR-UV-Vis and tested in the transesterification of sunflower and rapeseed vegetable oils at low temperatures, under different experimental conditions: autoclave, microwave and ultrasound. Working with these materials under microwave conditions provided higher conversions and selectivities to methylesters compared to autoclave or ultrasound conditions. Under ultrasound, a leaching of the magnesium has been evidenced as a direct consequence of a saponification reaction. These systems also allow working with much lower ratios of methanol to vegetable oil than reported in the literature for other heterogeneous systems. The activation temperature providing the most active catalysts was found to vary depending on the exposed facet: for MgO(111) structures (i.e. MgO (I)) this was 773 K, while for MgO (110) and (100) (i.e. MgO (II) and MgO (III)) this was 583 K.

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Pure and europium (Eu(3+)) doped cerium dioxide (CeO(2)) nanocrystals have been synthesized by a novel oil-in-water microemulsion reaction method under soft conditions. In-situ X-ray diffraction and RAMAN spectroscopy, high-resolution transmission electron microscopy, UV/Vis diffuse-reflectance and Fourier transform infrared spectroscopy as well as time-resolved photoluminescence spectroscopy were used to characterize the nanaocrystals. The as-synthesized powders are nanocrystalline and have a narrow size distribution centered on 3 nm and high surface area of ~250 m(2) g(-1). Only a small fraction of the europium ions substitutes for the bulk, cubic Ce(4+) sites in the europium-doped ceria nanocrystals. Upon calcination up to 1000 °C, a remarkable high surface area of ~120 m(2) g(-1) is preserved whereas an enrichment of the surface Ce(4+) relative to Ce(3+) ions and relative strong europium emission with a lifetime of ~1.8 ms and FWHM as narrow as 10 cm(-1) are measured. Under excitation into the UV and visible spectral range, the europium doped ceria nanocrystals display a variable emission spanning the orange-red wavelengths. The tunable emission is explained by the heterogeneous distribution of the europium dopants within the ceria nanocrystals coupled with the progressive diffusion of the europium ions from the surface to the inner ceria sites and the selective participation of the ceria host to the emission sensitization. Effects of the bulk-doping and impregnation with europium on the ceria host structure and optical properties are also discussed.

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Pure and europium (Eu(3+)) doped ZrO(2) synthesized by an oil-in-water microemulsion reaction method were investigated by in situ and ex situ X-ray diffraction (XRD), ex situ Raman spectroscopy, high-resolution transmission electron microscopy (HRTEM), steady state and time-resolved photoluminescence (PL) spectroscopies. Based on the Raman spectra excited at three different wavelengths i.e. 488, 514 and 633 nm and measured in the spectral range of 150-4000 cm(-1) the correlation between the phonon spectra of ZrO(2) and luminescence of europium is clearly evidenced. The PL investigations span a variety of steady-state and time resolved measurements recorded either after direct excitation of the Eu(3+) f-f transitions or indirect excitation into UV charge-transfer bands. After annealing at 500 °C, the overall Eu(3+) emission is dominated by Eu(3+) located in tetragonal symmetry lattice sites with a crystal-field splitting of the (5)D(0)-(7)F(1) emission of 20 cm(-1). Annealing of ZrO(2) at 1000 °C leads to a superposition of Eu(3+) emissions from tetragonal and monoclinic lattice sites with monoclinic crystal-field splitting of 200 cm(-1) for the (5)D(0)-(7)F(1) transition. At all temperatures, a non-negligible amorphous/disordered content is also measured and determined to be of monoclinic nature. It was found that the evolutions with calcination temperature of the average PL lifetimes corresponding to europium emission in the tetragonal and monoclinic sites and the monoclinic phase content of the Eu(3+) doped ZrO(2) samples follow a similar trend. By use of specific excitation conditions, the distribution of europium on the amorphous/disordered surface or ordered/crystalline sites can be identified and related to the phase content of zirconia. The role of zirconia host as a sensitizer for the europium PL is also discussed in both tetragonal and monoclinic phases.

Gold nanoparticles supported on TiO 2 effect the detoxification of soman and VX nerve gases and yperite vesicant agent at room temperature upon visible light illumination.

Despite considerable research, the location of an aliovalent dopant into SnO2 nanoparticles is far to be clarified. The aim of the present study on trivalent lanthanide doped SnO2 is to differentiate between substitutional versus interstitial and surface versus bulk doping, delineate the bulk and surface defects induced by doping and establish an intrinsic dopant distribution. We evidence for the first time a complex distribution of intrinsic nature composed of substitutional isolated, substitutional associates with defects as well as surface centers. Such multi-modal distribution is revealed for Eu and Sm, while Pr, Tb and Dy appear to be distributed mostly on the SnO2 surface. Like the previously reported case of Eu, Sm displays a long-lived luminescence decaying in the hundreds of ms scale which is likely related to a selective interaction between the traps and the substitutional isolated center. Analyzing the time-gated luminescence, we conclude that the local lattice environment of the lattice Sn is not affected by the particle size, being remarkably similar in the ~2 and 20 nm particles. The photocatalytic measurements employed as a probe tool confirm the conclusions from the luminescence measurements concerning the nature of defects and the temperature induced migration of lanthanide dopants.