Marco Antonio Ocsachoque

In the present work, we studied the catalytic performance (activity and selectivity) of Pt supported on carbon systems and Pt modified with tin in the glycerol oxidation with H₂O₂ as the oxidising agent at atmospheric pressure, 60 °C, and base-free conditions. The glycerol conversion obtained with monometallic Pt catalyst was 37% and remained unchanged with the addition of Sn in a ratio Sn/Pt = 0.4. The two bimetallic PtSn catalysts were able to oxidise commercial glycerol to dihydroxyacetone (DHA), and the selectivity to DHA reached 97% for the bimetallic catalyst with better conversion. In the reaction with crude glycerol, the conversion obtained was around 40% for the three catalysts, and the major product observed was glyceric acid. Both dihydroxyacetone and glyceric acid are high added value products with potential applications in different areas such as organic chemistry, medical and cosmetics industries.

Molecular modelling studies were carried out at the DFT level of the adsorption of propane and propene on Ag surfaces as a model of the interaction of light hydrocarbons with Ag/ZrO₂ catalysts for catalytic combustion reactions. It was found that the most stable mode of adsorption of propene through its π system on Ag atom has energies consistent with chemisorption and generates an elongation of the C1=C2 bond, which would explain the increase in the activity of the catalysts as a function of its metallic charge. The results obtained from the DFT calculations explain the different types of interactions between propene and propane with the metallic surface. The propene is chemisorbed on the Ag surface, distorting its bonds and generating its activation. This would imply that a higher metallic charge in the catalyst would increase the number of active sites in which this activation occurs, generating a higher activity. In addition, with the addition of O, the binding energy between the propene and the metal surface increased. On the other hand, the presence of a metallic surface is not enough for the activation of the propane molecule. This would explain why, by increasing the amount of metal in the catalyst, the activity for the combustion of propane is practically not affected.

Palladium-modified Co-ZnAland Cu-ZnAl materials were used and found active for the catalytic oxidation of propene and propane. According to the results obtained by XRD, TPR and XPS, the zinc aluminate-supported phases are oxide phases, Co₃O₄, CuO and PdO_x for Co-ZnAl, Cu-ZnAl and Pd-ZnAl catalysts, respectively. These reducible oxide species present good catalytic activity for the oxidation reactions. The addition of palladium to Co-ZnAl or Cu-ZnAl samples promoted the reducibility of the system and, consequently, produced a synergic effect which enhanced the activity for the propene oxidation. The PdCo-ZnAl sample was the most active and exhibited highly dispersed PdO_x particles and surface structural defects. In addition, it exhibited good catalytic stability. The H₂ pre-treated PdCu-ZnAl, PdCo-ZnAl and Pd-ZnAl samples showed higher activity than the original oxide catalysts, evidencing the important role of the oxidation state of the species, mainly of the palladium species, on the catalytic activity for the propene combustion. The synergic effect between metal transition oxides and PdO_x could not be observed for the propane oxidation.

Zirconia-supported gold-promoted cobalt catalysts were synthesized and tested for the complete oxidation of propane and naphthalene. The catalysts were characterized by BET surface area, scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), powder X-ray diffraction (XRD), transmission electron microscopy (TEM), temperature-programmed reduction (TPR), and X-ray photoelectron spectroscopy (XPS). In both propane and naphthalene combustion reactions, the results obtained indicate that catalysts formulated with Co₃O₄ are more active than those containing only Au. Catalysts prepared using the deposit/precipitation (DP) method have better activity than those in which the traditional technique is used. Gold addition using the DP methods generates a promoting effect on the activity of cobalt-containing catalysts. The AuDpCoZt catalyst was found to be the most active for both propane and naphthalene combustion. The catalytic behavior of this sample is associated with a synergic effect between gold, cobalt, and the support, which is also evidenced by an increase in the reducibility of this catalytic system. The effect of the presence of NO in the feed was also analyzed for propane combustion.

This work presents the physicochemical characterization and activity of zirconia-supported silver catalysts for the oxidation of pollutants present in diesel engine exhaust (propane, propene, naphthalene and soot). A series of silver-supported catalysts AgxZ (x = 1, 5 and 10 wt.%, Z = zirconia) were prepared, which were studied by various characterization techniques. The results show that silver is mainly found under the form of small metal nanoparticles (x oxidic phases. Silver is introduced onto the zirconia, generating Ag–ZrO₂ catalysts with high activity for the oxidation of propene and naphthalene. These catalysts also show some activity for soot combustion. Silver species can contribute with zirconia in the catalytic redox cycle, through a synergistic effect, providing sites that facilitate the migration and availability of oxygen, which is favored by the presence of structural defects. This is a novel application of the AgO_x–Ag/ZrO₂ system in the combustion reaction of propene and naphthalene. The results are highly promising, given that the T50 values found for both model molecules are quite low.

ZrO₂ nH₂O (hydrogel) impregnated with transition metals (Cu, Co, and Ni) was studied in this work as a precursor for the synthesis of CuO/ZrO₂ (CuZ), CoO_x/ZrO₂ (CoZ), and NiO/ZrO₂ (NiZ) catalysts, employed in the naphthalene oxidation reaction. Fresh and catalytically used materials were characterized by different physicochemical techniques, to compare the bulk and surface behavior, with particular attention to the effect of the supported metal species’ properties on the catalytic activity. Techniques such as X-ray diffraction (XRD), temperature programmed reduction (TPR), differential scanning calorimetry (DSC), Brunauer–Emmett–Teller (BET) surface area analyzer, diffuse reflectance spectroscopy (DRS UV–vis), and Raman spectroscopy, allow for establishing structural and textural aspects of the support, as well as the surface coordination and the accessibility of supported species. Results were in agreement with the CuZ > CoZ > NiZ sequence for the activity in naphthalene oxidation reaction. Electronic properties, ionic sizes, oxide phase deposition on the support surface, reducibility, metal–support interaction, and local site symmetry of metals seem to be decisive factors for the catalytic interaction with the gaseous phase.