Nanocrystalline brookite with enhanced stability and photocatalytic activity: influence of lanthanum(III) doping.

Metastable TiO(2) polymorphs are more promising materials than rutile for specific applications such as photocatalysis or catalysis support. This was clearly demonstrated for the anatase phase but still under consideration for brookite, which is difficult to obtain as pure phase. Moreover, the surface doping of anatase with lanthanum ions is known to both increase the thermal stability of the metastable phase and improve its photocatalytic activity. In this study, TiO(2) nanoparticles of almost only the brookite structure were prepared by a simple sol-gel procedure in aqueous solution. The nanoparticles were then doped with lanthanum(III) ions. The thermal stability of the nanoparticles was analyzed by X-ray diffraction and kinetic models were successfully applied to quantify phases evolutions. The presence of surface-sorbed lanthanum(III) ions increased the phase stability of at least 200 °C and this temperature shift was attributed to the selective phase stabilization of metastable TiO(2) polymorphs. Moreover, the combination of the surface doping ions and the thermal treatment induces the vanishing of the secondary anatase phase, and the photocatalytic tests on the doped brookite nanoparticles demonstrated that the doping increased photocatalytic activity and that the extent depended on the duration of the sintering treatment.

Use of polyols as particle size and shape controllers: application to boehmite synthesis from sol-gel routes.

Polyols were successfully used as size and shape controllers of oxide nanoparticles synthesized by soft chemistry in aqueous solution. The efficiency of acyclic polyols as a complexing agent depends obviously on the number of OH groups bonded to the carbon chain (and thus on the carbon chain length), but also on their stereochemistry. This innovating way to control morphology has been experienced for the synthesis of boehmite nanoparticles, whose morphology variations related to xylitol adsorption (C5 alditol) have been previously reported. The use of polyols during synthesis causes a modification of the usual morphologies observed, specifically resulting in an increase of (101) faces area. It is evidenced here that the variations of the nanoparticle aspect ratio are related to polyol complexing ability, and more specifically to molecule topology and configuration. Indeed, the morphology variations increase as a function of polyol carbon chain length and number of hydroxyl groups, and is much pronounced for stereoisomers exhibiting hydroxyl groups all oriented on the same side of the molecule (threo-threo sequences). Thanks to these various polyols used, we showed how the progressive levels of complexing ability allow us to tune boehmite particle size and shape. Material characterizations were performed using relevant methods such as X-ray diffraction powder pattern simulation and zetametry in addition to transmission electron microscopy. Since γ-alumina is obtained from boehmite by a topotactic transformation, we expect that this method will provide a promising way to control surface properties of γ-alumina, an important industrial catalyst support.

Growth of boehmite particles in the presence of xylitol: morphology oriented by the nest effect of hydrogen bonding.

The ability to design nanoparticles size and shape through the addition of simple and commercially available organic molecules is of particular interest in the catalytic domain because huge amounts of very fine powders are needed. The origin of this effect is all the more difficult to elucidate because the involved interactions are weak. In this paper, we have investigated the shaping of boehmite AlO(OH) nanoparticles in the presence of polyols like xylitol (C(5) alditol) by a combined experimental and theoretical approach. Experimental techniques such as XRD, TEM, IEP measurements, adsorption isotherms measurements, and (13)C MAS NMR experiments demonstrate that the effect of xylitol has a thermodynamic origin and suggest weak interactions between xylitol and the surface. Furthermore, the strongest proportion of lateral faces ((100), (001), and (101)) that of basal face would be in agreement with a preferential adsorption upon lateral surfaces. These results were refined by a computational approach. DFT calculations of surface energies (taking into account temperature and solvation effects) and of NMR shielding constants corroborate that molecular adsorption mode is preferred over all adsorption modes involving exchanges with surface OH groups. The preferred adsorption on lateral surfaces is attributed to the nest effect induced by hydroxyl groups localized on the concavities of the (001) and (101) surfaces, able to stabilize the xylitol molecule by hydrogen-bonding, whereas the basal (010) surface is almost flat. This combined experimental and computational approach thus provides interesting rationalization for the morphology effects observed.