No abstract

No abstract

Aerogels with their low density and high surface area are fascinating materials. However, their advantageous morphology is still far from being fully exploited owing to their limited compositional variety and low crystallinity. Replacing the sol-gel process by a particle-based assembly route is a powerful alternative to expand the accessible functionalities of aerogels. A strategy is presented for the controlled destabilization of concentrated dispersions of BaTiO3 nanoparticles, resulting in the assembly of the fully crystalline building blocks into cylindrically shaped monolithic gels, thereby combining the inherent properties of ternary oxides with the highly porous microstructure of aerogels. The obtained aerogels showed an unprecedentedly high surface area of over 300 m(2)  g(-1).

Texturing of magnetic ceramics and composites by aligning and fixing of colloidal particles in a magnetic field is a powerful strategy to induce anisotropic chemical, physical and especially mechanical properties into bulk materials. If porosity could be introduced, anisotropically structured magnetic materials would be the perfect supports for magnetic separations in biotechnology or for magnetic field-assisted chemical reactions. Aerogels, combining high porosity with nanoscale structural features, offer an exceptionally large surface area, but they are difficult to magnetically texture. Here we present the preparation of anatase-magnetite aerogel monoliths via the assembly of preformed nanocrystallites. Different approaches are proposed to produce macroscopic bodies with gradient-like magnetic segmentation or with strongly anisotropic magnetic texture.

Defect engineering operated on metal oxides by chemical and structural modifications may strongly affect properties suitable for various applications such as photoelectrochemical behaviour, charge transport and luminescence. In this work we report the tuneable optical features observed in undoped monoclinic HfO 2 nanocrystals and their dependence on the structural properties of the material at the nanoscale. Transmission electron microscopy together with X-ray diffraction and surface area measurements were used to determine the fine structural modifications, in terms of crystal growth and coalescence of crystalline domains, occurring during a calcination process in the temperature range from 400 to 1000 °C. The fit of the broad optical emission into spectral components, together with time resolved photoluminescence, allowed us to identify the dual nature of the emission at 2.5 eV, where an ultrafast defect-related intrinsic luminescence (with decay time of few ns) overlaps with a slower emission (decay of several µs) due to extrinsic Ti -impurity centres. Moreover, the evolution of intrinsic visible bands during the material transformation was monitored. The relationship between structural parameters uniquely occurring in nanosized materials and the optical properties was investigated and tentatively modelled. The blue emissions at 2.5 and 2.9 eV are clearly related to defects lying at crystal boundaries, while an unprecedented emission at 2.1 eV enables, at relatively low calcination temperatures, the white luminescence of HfO 2 under near-UV excitation.