National Institute Of Materials Physics - Romania

TEMPO stable free radical has been supported on porous silica nanoparticles in different ways and the resulted materials have been tested as heterogeneous oxidation catalyst of three benzylic alcohols using air as final oxidant and nitrosonium tetrafluoroborate as cocatalyst. Good to excellent yields were obtained. The catalytic system consists in fact in two coupled cycles, NO/NO2 and TEMPO+/TEMPO, able to convert under mild conditions (room temperature, air, metal and halogen free condition) alcohols into aldehydes or ketones. Under these conditions, supported TEMPO on silica nanoparticles containing gold clusters lowers the efficiency of the catalyst.

A bimodal (micro/mesoporous) COF was synthesized by coupling tetrakis-1,3,5,7-(4'-iodophenyl) adamantane with 4,4'-diethynylbiphenyl following a Sonogashira protocol. The COF preparation strategy led, however, to the incomplete recovery of the palladium catalyst and ICP-OES analysis indicated that around 0.1 wt% palladium remained inside the pores. Noteworthily, the remnant palladium catalyst is still accessible and can be valorised in additional catalytic reactions like the hydrogenation of nitrostyrene. Further deposition of 0.5 wt% active metals (like palladium or gold) enhanced the catalytic activity and tuned the catalyst selectivity with respect to analogous metal catalysts prepared using active carbon as a support. The resulting COF-supported metal NPs are stable and recyclable catalysts. Under normal conditions, this COF is also able to adsorb large amounts of weak electrophilic gases like carbon dioxide.

We report the applicability of a hybrid system comprising a La3+-based catalyst and an Au/TiO2 photocatalyst in the decomposition of chemical weapons. This system is able to perform complete degradation of soman, sarin and VX in less than 1 minute under low basic conditions and visible light irradiation.

Ni-doped (CeO2-delta)-YSZ (5 mol% Ni oxide, 10 mol% ceria) mesoarchitectures (MA) with nanocrystalline framework have been synthesized by an original, facile and cheap approach based on Triton X100 nonionic surfactant as template and water as solvent at a strong basic pH value. Following the hydrothermal treatment under autogenous pressure (similar to 18 bars), Ni, Ce, Y, and Zr were well ordered as MA with nanocrystalline framework, assuring thermal stability. A comprehensive investigation of structure, texture, morphology, and surface chemistry was performed by means of a variety of complementary techniques (X-Ray Diffraction, XRD; Raman Spectroscopy, RS; Brunauer-Emmett-Teller, BET; Temperature-Programmed Reduction, TPR; Transmission Electron Microscopy, TEM and DF-STEM; X-ray Photoelectron Spectroscopy, XPS; Catalytic activity and selectivity). N-2 sorption measurements highlighted that the mesoporous structure is formed at 600 degrees C and remains stable at 800 degrees C. At 900 degrees C, the MA collapses, favoring the formation of macropores. The XRD and Raman Spectroscopy of all samples showed the presence of a pure, single phase with fluorite-type structure. At 900 degrees C, an increased tetragonal distortion of the cubic lattice was observed. The surface chemistry probed by XPS exhibits a mixture of oxidation states (Ce3+ + Ce4+) with high percentage of Ce3+ valence state similar to 35 % and (Ni3+ and Ni2+) oxidation states induced by the thermal treatment. These nanoparticles assembled into MA show high stability and selectivity over time in catalytic partial oxidation of methane (CPOM). These promising performances suggest an interesting prospect for introduction as anode within IT-SOFC assemblies.