A simple processing route to nanostructured mixed cobalt−nickel molybdates, Co1 - x Ni x MoO4 (0 ≤ x ≤ 1), has been developed. It is based on the use of precursors resulting from the freeze-drying of aqueous solutions of the appropriate common metal salts. Thermal decomposition of amorphous freeze-dried powders at low temperatures produces the nanostructured mixed oxides. A study of the influence of the preparative variables on the outcomes of this procedure is presented. The resulting materials have been characterized by X-ray powder diffraction, elemental analysis, scanning electron microscopy, thermogravimetry under oxygen flow, and physisorption measurements. Co1 - x Ni x MoO4 grains (obtained by calcination below 773 K) are aggregates of nanometric particles (with diameters typically around 30−40 nm) and have relatively high specific surface areas (20−40 m2/g). The catalytic activity of the nanostructured cobalt and nickel molybdates for the oxidative dehydrogenation of propane has been evaluated. The performance of these nanostructured catalysts in this process is higher than those reported for homologous oxides prepared through conventional procedures.

We report diffuse reflectivity measurements in InNbO4, ScNbO4, YNbO4, and eight rare-earth niobates. A comparison with established values of the bandgap of InNbO4 and ScNbO4 shows that Tauc plot analysis gives erroneous estimates of the bandgap energy. Conversely, accurate results are obtained considering excitonic contributions using the Elliot–Toyozawa model. The bandgaps are 3.25 eV for CeNbO4, 4.35 eV for LaNbO4, 4.5 eV for YNbO4, and 4.73–4.93 eV for SmNbO4, EuNbO4, GdNbO4, DyNbO4, HoNbO4, and YbNbO4. The fact that the bandgap energy is affected little by the rare-earth substitution from SmNbO4 to YbNbO4 and the fact that they have the largest bandgap are a consequence of the fact that the band structure near the Fermi level originates mainly from Nb 4d and O 2p orbitals. YNbO4, CeVO4, and LaNbO4 have smaller bandgaps because of the contribution from rare-earth atom 4d, 5d, or 4f orbitals to the states near the Fermi level.

The structural stability and physical properties of CrVO4 under compression were studied by x-ray diffraction, Raman spectroscopy, optical absorption, resistivity measurements, and ab initio calculations up to 10 GPa. High-pressure x-ray diffraction and Raman measurements show that CrVO4 undergoes a phase transition from the ambient pressure orthorhombic CrVO4-type structure (Cmcm space group, phase III) to the high-pressure monoclinic CrVO4-V phase, which is proposed to be isomorphic to the wolframite structure. Such a phase transition (CrVO4-type → wolframite), driven by pressure, also was previously observed in indium vanadate. The crystal structure of both phases and the pressure dependence in unit-cell parameters, Raman-active modes, resistivity, and electronic band gap, are reported. Vanadium atoms are sixth-fold coordinated in the wolframite phase, which is related to the collapse in the volume at the phase transition. Besides, we also observed drastic changes in the phonon spectrum, a drop of the band-gap, and a sharp decrease of resistivity. All the observed phenomena are explained with the help of first-principles calculations.

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Silica-based rigid monoliths exhibiting a trimodal hierarchical pore system have been successfully prepared through coating of a ceramic foam (CF) with sub-micro-/nanometric mesoporous particles (as building blocks). We have selected a bimodal porous silica, denoted as UVM-7 (a nanometric version of the well-known MCM-41 materials), consisting of small aggregates of nanometric surfactant-assisted mesoporous particles. A colloidal suspension of this material in water is used to coat through successive impregnation cycles the CF surface. The small intraparticle mesopore system (with pore diameters around 2-3 nm) is due to the supramolecular templating effect of the surfactant. Textural large-mesopores/ macropores (in the 20-70 nm range) have their origin in the interparticle UVM-7 voids. The large macrocellular macropores are due to the CF support. The resulting monoliths present a good and homogeneous coverage level. Moreover, these composites display better mechanic properties than those of related silica self-supported monoliths.