A New Supramolecular Tetraruthenated Cobalt (II) Porphyrazine Displaying Outstanding Electrocatalytical Performance in Oxygen Evolution Reaction.

A new supramolecular electrocatalyst for Oxygen Evolution Reaction (OER) was synthesized from a central multibridging cobalt tetrapyridylporphyrazine (CoTPyPz) species by attaching four [Ru(bpy)2Cl]+ groups. Both CoTPyPz and the tetraruthenated cobalt porphyrazine species, TRuCoTPyPz, form very homogenous molecular films just by dropcasting their methanol solutions onto GCE electrodes. Such films exhibited low overpotentials for O2 evolution, e.g., 560 e 340 mV, respectively, displaying high stability, typically exceeding 15 h. The kinetic parameters obtained from the Tafel plots showed that the peripheral complexes are very important for the electrocatalytic activity. Hyperspectral Raman images taken along the electrochemical process demonstrated that the cobalt center is the primary active catalyst site, but its performance is enhanced by the ruthenium complexes, which act as electron-donating groups, in the supramolecular system.

Phosphotungstic acid impregnated niobium coated superparamagnetic iron oxide nanoparticles as recyclable catalyst for selective isomerization of terpenes.

Conversion efficiency as high as 80-100% and 50% selectivity for camphene and limonene was achieved with low production of polymeric byproducts (18-28%), easy recovery with a magnet and reuse for up to five cycles maintaining similar activity and distribution of products, using a new magnetically recyclable catalyst based on niobium oxide coated on superparamagnetic iron oxide nanoparticles (SPION) impregnated with phosphotungstic acid (HPW). The catalyst was demonstrated to be effective in the selective conversion of alpha and beta-pinenes into valuable terpenes, under ultrasonic probe activation and with toluene as solvent. A unique synergic effect between the components generating more active and selective catalytic sites was demonstrated, indicating that the SPION covered with 30 wt% of Nb2O5 gives the best performance when impregnated with HPW as co-catalyst. The materials were fully characterized by XRD, EDX, XPS, TEM, BET, VSM and FTIR.

Superparamagnetic iron oxide nanoparticles (SPIONs) conjugated with lipase Candida antarctica A for biodiesel synthesis.

Biodiesel is an alternative biodegradable and non-toxic fuel, with a low emission profile and capable of reducing significantly the level of carcinogenic pollutants released into the atmosphere. A newly designed nano-biocatalyst prepared by conjugation of lipase A on superparamagnetic iron oxide nanoparticles (SPIONs) demonstrated high efficiency for production of biodiesel by the reaction of soybean oil with anhydrous methanol. The nanomaterial was characterized by FTIR, TGA and XRD, and its enzymatic activity compared with Lipozyme 435, a commercial gold standard from Novozyme™, which presented average enzymatic activity of 4559 ± 75 only twice as large as that of the SPION-CAL-A catalyst (2283 ± 249 PLU g-1), whereas Lipozyme TLIM showed a much lower activity of 588 ± 16 PLU g-1. These results were confirmed in the transesterification reaction for production of biodiesel where a yield of 11.4% was achieved with Lipozyme 435 and 4.6 ± 0.5% with the nano-biocatalyst. Such an improved performance associated with easy magnetic recovery and reuse make the material potentially interesting for production of biodiesel from used cooking oil, adding value to this abundant resource.