Catalytic wet air oxidation of high BPA concentration over iron-based catalyst supported on orthophosphate.

The catalytic performance of Fe supported on nickel phosphate (NiP) was evaluated for the removal of bisphenol A (BPA) by catalytic wet air oxidation (CWAO) at 140 °C and 25 bar of pure oxygen pressure. The prepared NiP and Fe/NiP materials were fully characterized by XRD, N2-physisorption, H2-TPR, TEM, and ICP analysis. Iron (Fe/NiP) impregnation of NiP support enhanced the BPA removal efficiency from 37.0 to 99.6% when CWAO was performed. This catalyst was highly stable given the operating conditions of acidic medium, high temperature, and high pressure. The Fe/NiP catalyst showed an outstanding catalytic activity for oxidation of BPA, achieving almost complete removal of BPA in 180 min at a concentration of 300 mg/L, using 4 g/L of Fe/NiP. No iron leaching was detected after the CWAO of BPA. The stability of Fe/NiP was performed over three consecutive cycles, noting that BPA conversion was not affected and iron leaching was negligible. Therefore, this catalyst (Fe/NiP) could be considered as an innocuous and effective long-lasting catalyst for the oxidation of harmful organic molecules.

Supported Co-Re Bimetallic Catalysts with Different Structures as Efficient Catalysts for Hydrogenation of Citral.

Bimetallic Co-Re/TiO2 catalysts were developed for efficient citral hydrogenation. Bimetallic catalysts were prepared by co-impregnation (CI), successive-impregnation (SI), and surface redox method (SR). The arrangement between the Co and Re species on these systems was fully characterized using several techniques (TEM-energy-dispersive X-ray spectroscopy, H2 temperature-programmed reduction, temperature-programmed desorption, XRD, CO FTIR spectroscopy, model reaction of cyclohexane dehydrogenation), and their catalytic performances were evaluated for the selective hydrogenation of citral towards unsaturated alcohols. The Re and Co species are completely isolated in the CI sample, presenting a very limited Co-Re interaction. In SI samples, the metals coexist in a Janus-type structure with a concentration of Re around Co. Decoration/core-shell structures are observed for SR samples resulting from the redox exchange between the metallic surface of the parent Co/TiO2 catalyst and the Re7+ species of the modifier precursor salt. The contact degree between the two metals gradually increases as follows: Isolated structure (CI)

EXAFS characterization of dendrimer-Pt nanocomposites used for the preparation of Pt/gamma-Al2O3 catalysts.

Pt/gamma-Al2O3 catalysts were prepared using hydroxyl-terminated generation four (G4OH) PAMAM dendrimers as the templating agents and the various steps of the preparation process were monitored by extended X-ray absorption fine structure (EXAFS) spectroscopy. The EXAFS results indicate that, upon hydrolysis, chlorine ligands in the H(2)PtCl(6) and K(2)PtCl(4) precursors were partially replaced by aquo ligands to form [PtCl3(H2O)3]+ and [PtCl2(H2O)2] species, respectively. The results further suggest that, after interaction of such species with the dendrimer molecules, chlorine ligands from the first coordination shell of Pt were replaced by nitrogen atoms from the dendrimer interior, indicating that complexation took place. This process was accompanied by a substantial transfer of electron density from the dendrimer to platinum, indicating that the dendrimer plays the role of a ligand. Following treatment of the H(2)PtCl(6)/G4OH and K(2)PtCl(4)/G4OH complexes with NaBH4, no substantial changes were observed in the electronic or coordination environment of platinum, indicating that metal nanoparticles were not formed during this step under our experimental conditions. However, when the reduction treatment was performed with H2, the formation of extremely small platinum clusters, incorporating no more than four Pt atoms was observed. The nuclearity of these clusters depends on the length of the hydrogen treatment. These Pt species remained strongly bonded to the dendrimer. Formation of larger platinum nanoparticles, with an average diameter of approximately 10 A, was finally observed after the deposition and drying of the H(2)PtCl(6)/G4OH nanocomposites on a gamma-Al(2)O(3) surface, suggesting that the formation of such nanoparticles may be related to the collapse of the dendrimer structure. The platinum nanoparticles formed appear to have high mobility because subsequent thermal treatment in O2/H2, used to remove the dendrimer component, led to further sintering.

Particle size control in dendrimer-derived supported ruthenium catalysts.

A high-resolution transmission electron microscopy (HRTEM) investigation of a family of supported Ru catalysts prepared from Ru hydroxyl-terminated poly(amidoamine) dendrimer-metal nanocomposite (DMN) precursors has been conducted. Ru particle sizes observed following deposition of DMNs on a HRTEM grid can be controlled within a 0.9-1.4 nm range depending on the metal-to-dendrimer molar ratio. The average particle size in this case correlates well with the theoretically predicted particle size from the molar loading of Ru in the dendrimer. Upon impregnation of Ru-DMNs on Al(2)O(3) and subsequent thermal removal of the dendrimer via reduction at 300 degrees C, significant sintering of the Ru particles was observed. Nevertheless, the resulting supported Ru particles maintained a narrow particle size distribution and average particle size below 2.5 nm. These particle sizes no longer correlate with the metal-to-dendrimer molar ratio but do correlate with the metal-to-dendrimer weight ratio, suggesting that the dendrimer may be acting as a "sintering-control" agent on the catalyst surface. This process is not affected by the surface area of the support, since almost identical particle size distributions were obtained on three different commercial supports.

FTIR studies of CO adsorption on Rh-Ge/Al2O3 catalysts prepared by surface redox reactions.

A series of bimetallic Al2O3-supported Rh-Ge catalysts was prepared by surface redox reactions under controlled hydrogen atmosphere. The surface properties of these catalysts were probed via in-situ FTIR spectroscopic studies of adsorbed CO and were compared to those of monometallic Rh catalysts that had undergone similar treatments. The results indicate that Ge addition results in the formation and stabilization of smaller rhodium ensembles at the expense of larger Rh0 surfaces. A charge-transfer mechanism from Ge to Rh is also inferred by the IR results for the high Ge loading samples. Air exposure of the catalysts leads to an irreversible segregation of the two metals and formation of large Rh crystallites.