Magnetic Aerogels for Room-Temperature Catalytic Production of Bis(indolyl)methane Derivatives.

The potential of aerogels as catalysts for the synthesis of a relevant class of bis-heterocyclic compounds such as bis(indolyl)methanes was investigated. In particular, the studied catalyst was a nanocomposite aerogel based on nanocrystalline nickel ferrite (NiFe2O4) dispersed on amorphous porous silica aerogel obtained by two-step sol-gel synthesis followed by gel drying under supercritical conditions and calcination treatments. It was found that the NiFe2O4/SiO2 aerogel is an active catalyst for the selected reaction, enabling high conversions at room temperature, and it proved to be active for three repeated runs. The catalytic activity can be ascribed to both the textural and acidic features of the silica matrix and of the nanocrystalline ferrite. In addition, ferrite nanocrystals provide functionality for magnetic recovery of the catalyst from the crude mixture, enabling time-effective separation from the reaction environment. Evidence of the retention of species involved in the reaction into the catalyst is also pointed out, likely due to the porosity of the aerogel together with the affinity of some species towards the silica matrix. Our work contributes to the study of aerogels as catalysts for organic reactions by demonstrating their potential as well as limitations for the room-temperature synthesis of bis(indolyl)methanes.

Nanostructured Ni/CeO2-ZrO2 Catalysts for CO2 Conversion into Synthetic Natural Gas.

NiO-CeO2-ZrO2 mixed oxides, with Ni/(Ce + Zr) = 1 mol/mol and different Ce/Zr molar ratios, were prepared by the soft-template method. The chemical composition, texture, structure, and redox features of the synthesized systems were investigated by different techniques. All samples were nanocrystalline (NiO nanocrystal average size 4 nm) and had high surface area and quite an ordered mesoporous system. The catalytic performances in the CO2 conversion into methane were studied at atmospheric pressure, 300 °C, and stoichiometric H2/CO2 molar ratio. Prior to reaction the catalysts were submitted to a mild reduction pretreatment (H2 at 400 °C for 1 h). XRD analysis of the samples after pretreatment showed the presence of small Ni crystals (4-7 nm) on all the samples as well as of some unreduced NiO nanocrystals on the systems with high Zr content, in accordance with H2-TPR experiments, which indicated that NiO reduction is promoted by CeO2 but hindered by ZrO2. The catalytic tests were performed at two different space velocities (72000 and 900000 cm³ h-1 g-1cat) on a series of Ni-based catalysts supported on CeO2-ZrO2 systems with different Ce/Zr ratios, including the two pure oxides. CO2 conversion and selectivity to CH4 (which was always close to 100 mol%) were constant throughout the 6-hour runs. CO2 conversion resulted to increase with CeO2 content in the catalyst, thus indicating the role of the CeO2 component of the support in activating CO2, whereas H2 is activated on the Ni nanoparticles.