Carolina Blanco

En este trabajo se lleva a cabo la síntesis y caracterización de catalizadores tipo salen con Zn, los cuales son obtenidos mediante reacción de condensación entre una 1,2-diamina y 3,5-diterc-butilsalicilaldehído en presencia de acetato de zinc. Se obtuvieron rendimientos del 86% en la síntesis del catalizador Zn-salen-1, 60% para Zn-salen-2 y 70% para Zn-salen-3. Estos catalizadores fueron usados en la reacción de acoplamiento de óxido de limoneno con CO2. Los mejores resultados en términos de conversión (20%) se evidenciaron cuando el sistema catalítico Zn-salen-2/NBuI se evaluó usando 20 bar de CO2, 40°C durante 24 h. En todos los casos studiados, la reacción demostró ser completamente selectiva hacia la formación del policarbonato de limoneno. No se encontró dependencia significativa de la presión de CO2 en la determinación de la actividad del sistema catalítico examinado.

In this work, the significant intensification of a bentonite pillaring process was achieved by using a novel methodological approach, leading to an intercalating Al/Fe mixed oligomeric precursor, around 100 times more concentrated than usually reported. In addition, the intercalating step was achieved directly on the clay with no previous swelling of the mineral being required; this allowed the successful scaled-up preparation of the Al/Fe-PILC, by a factor of one thousand, from the lab (10 g) to the pilot scale (10 kg). Intercalating solutions prepared under either concentrated (13 cm³) or diluted (widely reported, 2.0 dm³) conditions for lab-scale preparations were both translucent, displaying similar final pH values (close to 4.0) typical of highly oligomerized Al-pillaring solutions. The clay modified from concentrated precursors at the 10 g scale reached a high basal spacing (18.3 Å) and specific surface area (198 m² g⁻¹) with very comparable fractions of Fe forming truly mixed Al/Fe pillars in comparison to a reference material (H₂-TPR analyses). This promoted high performance in the catalytic wet peroxide oxidation of phenol in aqueous solution as a toxic model organic molecule at very mild temperature (25.0 °C ± 1.0 °C) and pressure (76 kPa), exhibiting the highest catalytic efficiency as a function of both parameters (full conversion of phenol together with 45.2% of TOC mineralization) with low iron leaching using a very low catalyst concentration (0.25 g dm⁻³). Particle size refining of the starting clay, the speed of stirring and conditions for the final washing of the interlayered precursor are the main factors influencing successful pillaring at scales higher than 1.0 kg.

Four natural clays were modified with mixed polyoxocations of Al/Fe for evaluating the effect of the physicochemical properties of the starting materials (chemical composition, abundance of expandable clay phases, cationic exchange capacity and textural properties) on final physicochemical and catalytic properties of Al/Fe-PILCs. The aluminosilicate denoted C2 exhibited the highest potential as starting material in the preparation of Al/Fe-PILC catalysts, mainly due to its starting cationic exchange capacity (192 meq/100 g) and the dioctahedral nature of the smectite phase. These characteristics favored the intercalation of the mixed (Al_13−x/Fe_x)⁷⁺ Keggin-type polyoxocations, stabilizing a basal spacing of 17.4 Å and high increase of the BET surface (194 m²/g), mainly represented in microporous content. According to H₂-TPR analyses, catalytic performance of the incorporated Fe in the Catalytic Wet Peroxide Oxidation (CWPO) reaction strongly depends on the level of location in mixed Al/Fe pillars. Altogether, such physicochemical characteristics promoted high performance in CWPO catalytic degradation of methyl orange in aqueous medium at very mild reaction temperatures (25.0 ± 1.0 °C) and pressure (76 kPa), achieving TOC removal of 52% and 70% of azo-dye decolourization in only 75 min of reaction under very low concentration of clay catalyst (0.05 g/L).