Probing the catalytic activity of sulfate-derived Pristine and post-treated porous TiO2(101) anatase mesocrystals by the oxidative desulfurization of dibenzothiophenes

Mesocrystals (basically nanostructures showing alignment of nanocrystals well beyond crystal size) are attracting considerable attention for modeling and optimization of functionalities. However, for surface-driven applications (heterogeneous catalysis), only those mesocrystals with excellent textural properties are expected to fulfill their potential. This is especially true for oxidative desulfuration of dibenzothiophenes (hard to desulfurize organosulfur compounds found in fossil fuels). Here, we probe the catalytic activity of anatases for the oxidative desulfuration of dibenzothiophenes under atmospheric pressure and mild temperatures. Specifically, for this study, we have taken advantage of the high stability of the (101) anatase surface to obtain a variety of uniform colloidal mesocrystals (approximately 50 nm) with adequate orientational order and good textural properties (pores around 3-4 nm and surface areas around 200 m2/g). Ultimately, this stability has allowed us to compare the catalytic activity of anatases that expose a high number of aligned single crystal-like surfaces while differing in controllable surface characteristics. Thus, we have established that the type of tetrahedral coordination observed in these anatase mesocrystals is not essential for oxidative desulfuration and that both elimination of sulfates and good textural properties significantly improve the catalytic activity. Furthermore, the most active mesocrystals have been used to model the catalytic reaction in three-(oil-solvent-catalyst) and two-phase (solvent-catalyst) systems. Thus, we have been able to observe that the transfer of DBT from the oil to the solvent phase partially limits the oxidative process and to estimate an apparent activation energy for the oxidative desulfuration reaction of approximately 40 kJ/mol in the two-phase system to avoid mass transfer limitations. Our results clearly establish that (101) anatase mesocrystals with excellent textural properties show adequate stability to withstand several post-treatments without losing their initial mesocrystalline character and therefore could serve as models for catalytic processes different from the one studied here.Fil: Rivoira, Lorena Paola. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigación y Tecnología Química. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Tecnología Química; ArgentinaFil: Martinez, Maria Laura. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación en Nanociencia y Nanotecnología; ArgentinaFil: Falcon, Horacio. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación en Nanociencia y Nanotecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; ArgentinaFil: Beltramone, Andrea Raquel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación en Nanociencia y Nanotecnología; ArgentinaFil: Campos-Martin, Jose M.. Consejo Superior de Investigaciones Científicas; EspañaFil: García Fierro, José Luis. Instituto de Catalisis y Petroleoquimica-csic; EspañaFil: Tartaj, Pedro. Consejo Superior de Investigaciones Científicas. Instituto de Catálisis y Petroleoquímica; Españ

patrimonio intelectual

Actas de congresoLas VI Jornadas se realizaron con la exposición de ponencias que se incluyeron en cuatro ejes temáticos, que se desarrollaron de modo sucesivo para facilitar la asistencia, el intercambio y el debate, distribuidos en tres jornadas. Los ejes temáticos abordados fueron: 1. La enseñanza como proyecto de investigación. Recursos de enseñanza-aprendizaje como mejoras de la calidad educativa. 2. La experimentación como proyecto de investigación. Del ensayo a la aplicabilidad territorial, urbana, arquitectónica y de diseño industrial. 3. Tiempo y espacio como proyecto de investigación. Sentido, destino y usos del patrimonio construido y simbólico. 4. Idea constructiva, formulación y ejecución como proyecto de investigación. Búsqueda y elaboración de resultados que conforman los proyectos de la arquitectura y el diseño

Hydrodeoxygenation of guaiacol over Pt-Ga-mesoporous catalysts

The hydrodeoxygenation (HDO) of guaiacol as model compound has been studied in a batch reactor over SBA-15 and Ga-SBA-15 supported platinum catalysts at 12 atm of H2 and different temperatures. Gallium incorporation as heteroatom into the mesoporous siliceous framework modified the nature of the support generating Brønsted acidity. The catalysts were characterized by means of X-ray diffraction, N2 isotherms, XPS, TPR, CO chemisorptions, Py FTIR and TEM. Good structure, narrow pore size distribution and high platinum dispersion were achieved in the synthesized catalysts. The catalysts were very active in the conversion of guaiacol at 200 °C, almost complete conversion was obtained in 3 h of reaction. Mild acidity generated by gallium incorporation enhanced the dispersion of platinum active species and improve the HDO ratio.Fil: Rivoira, Lorena Paola. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación en Nanociencia y Nanotecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; ArgentinaFil: Martinez, Maria Laura. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación en Nanociencia y Nanotecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; ArgentinaFil: Beltramone, Andrea Raquel. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación en Nanociencia y Nanotecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentin

Experimental design optimization of the ODS of DBT using vanadium oxide supported on mesoporous Ga-SBA-15

Experiment design-response surface methodology is applied in this work to model and optimize the oxidation of dibenzothiophene (DBT) using VOx-Ga-SBA-15 catalyst. The analyzed variables are the influence of the nature of the catalyst (V and Ga loading), the substrate/catalyst mass ratio (g DBT/g of catalyst) and the oxidant/substrate molar ratio (H2O2/DBT). The response analyzed is conversion of DBT at 15 min of reaction time. A set of response surfaces were obtained applying the Box-Behnken Design. Based on statistical methodology it was possible to find the best arrangement between the amounts of the gallium heteroatom and the vanadium active species. The higher levels of the objective function were obtained employing the catalyst with 4 wt.% of gallium and 6 wt.% of vanadium; the optimal ratio between g DBT/g of catalyst was 4 and the molar ratio between H2O2/DBT was 5. Gallium incorporation as heteroatom in tetrahedral position allowed the better anchorage of the active species of vanadium, generating a very well dispersed catalyst. The optimized catalyst minimized the mass transfer limitation and moreover, was active after several recycles. The best catalyst was likewise very active for the oxidation of the most refractory sulfur compounds as benzothiophene and 4,6-dimetyldibenzothiopene.Fil: Rivoira, Lorena Paola. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Tecnología Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Cussa, Jorgelina. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación en Nanociencia y Nanotecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Martinez, Maria Laura. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación en Nanociencia y Nanotecnología; ArgentinaFil: Beltramone, Andrea Raquel. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación en Nanociencia y Nanotecnología; Argentin

Vanadium oxide supported on mesoporous SBA-15 modified with Al and Ga as a highly active catalyst in the ODS of DBT

Vanadium oxides supported on mesoporous SBA-15 catalysts with different vanadium loadings were studied in the oxidative desulfurization (ODS) of dibenzothiophene as a model sulfur compound. The catalytic activity was improved when SBA-15 framework was modified by adding Al and Ga. Structural and textural characterization of the catalysts were performed by means of XRD, N2 adsorption, UV–Vis–DRS, XPS, NMR, TEM, Raman, TPR and Py-FTIR. UV–Vis–DRS and Raman demonstrated that highly dispersed vanadium VO4 −3 species are responsible for the high activity in the sulfur removal. The Ga modified support with an intermediate V/Si ratio of 1/30 was the most active catalyst for ODS of DBT, using hydrogen peroxide as oxidant and acetonitrile as solvent. 100% of DBT elimination was attained at a short time in mild conditions. Gallium and aluminum incorporation into the support modified successfully the nature of the SBA-15 surface by generating Bronsted and Lewis acidity. The interaction between the acid sites with the active vanadium sites improved the activity of the catalysts. The high dispersion depended on the vanadium loading and on the nature of the support. The more acidic support allowed better dispersion of the vanadium species due to stronger interaction metal-support. The reusability of the catalysts indicates that vanadium oxide supported on mesoporous SBA-15 modified with Ga and Al are potential catalysts for the ODS of dibenzothiophene.Fil: Rivoira, Lorena Paola. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación en Nanociencia y Nanotecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; ArgentinaFil: Martinez, Maria Laura. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación en Nanociencia y Nanotecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Anunziata, Oscar Alfredo. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación en Nanociencia y Nanotecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Beltramone, Andrea Raquel. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación en Nanociencia y Nanotecnología; Argentin

Novel and simple one-pot method for the synthesis of TiO 2 modified-CMK-3 applied in oxidative desulfurization of refractory organosulfur compounds

Ti-CMK-3 carbon mesoporous was prepared using a novel synthesis method. This new method avoids the hard template synthesis used commonly. The precursors of silicon, carbon and titanium are incorporated together with the other components during the only step of the synthesis. The method developed here, allows reducing time and energy consumption by 60% and thus, the cost of the overall process of synthesis. Structural and textural characterization of the titanium modified-mesoporous carbon was performed by N2 adsorption, XRD, UV–Vis-DRS, XPS, Raman spectroscopy and TEM. The characterization results indicated that the textural and structural properties of the material synthesized by the short time method are comparable with the properties of the material prepared by the hard template method. Ti modified-mesoporous carbon was synthesized by different methods in order to prepare catalysts to be tested in the oxidative desulfurization (ODS) of sulfur compounds. The catalyst prepared by the one-pot method is capable to oxidize high amount of sulfur (2000 ppm) in only 30 min of reaction time at 60–80 °C. The good performance and stability of the catalyst prepared using a novel synthesis method was attributed to well dispersed anatase nanospecies over the high area mesoporous carbon. Main advantage of the present study is the reduction of time and cost in the synthesis of the new material and the applicability for ODS reactions.Fil: Rivoira, Lorena Paola. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación en Nanociencia y Nanotecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; ArgentinaFil: Ledesma, Brenda Cecilia Soledad. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación en Nanociencia y Nanotecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; ArgentinaFil: Juárez, Juliana M.. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación en Nanociencia y Nanotecnología; ArgentinaFil: Beltramone, Andrea Raquel. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación en Nanociencia y Nanotecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentin

Catalytic oxidation of sulfur compounds over Ce-SBA-15 and Ce-Zr-SBA-15

The catalytic oxidation of different sulfur compounds, commonly present in liquid fuel, was studied over a series of ceria and ceria-zirconium based oxidation mesoporous catalysts. SBA-15 was synthesized using sol-gel method and Ce and Ce-Zr were added by two different procedures: i) directly during the synthesis and ii) via post-synthesis method. The catalysts were characterized by XRD, N2 adsorption isotherms, XPS, DRUV-Vis, TEM, SEM and Py-FTIR. Low angle XRD, N2 isotherms and TEM confirmed that the structure was not changed after metal incorporation. Wide angle XRD, UV–vis-DRS, XPS and TEM determined that the catalysts prepared by direct synthesis presented higher dispersion of Ce oxides, smaller particle size and isolated Zr4+ species. FTIR of adsorbed/desorbed pyridine indicated that zirconium as promoter increases the Lewis acidity of the catalysts, especially during direct synthesis. Ce-Zr-SBA-15 catalyst prepared by direct synthesis was very active in the oxidation of dibenzothiophene, 4,6-dimethyl dibenzothiophene and benzothiophene using hydrogen peroxide (H2O2) as oxidant agent and acetonitrile as polar solvent. The effect of acidity in the catalyst, hydrogen peroxide concentration and temperature was studied. The deactivation test demonstrated that the catalyst is stable and adequate for the industrial process.Fil: Rivoira, Lorena Paola. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación y Tecnología Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Vallés, Verónica Alejandra. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación en Nanociencia y Nanotecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Martínez, María L.. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación en Nanociencia y Nanotecnología; ArgentinaFil: Sa-ngasaeng, Yanika. Chulalongkorn University; TailandiaFil: Jongpatiwut, Siriporn. Chulalongkorn University; TailandiaFil: Beltramone, Andrea Raquel. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación en Nanociencia y Nanotecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentin

Vanadium and titanium oxide supported on mesoporous CMK-3 as new catalysts for oxidative desulfurization

Vanadium supported-CMK-3 catalysts with vanadium loading of 1–7 wt.% were studied in the oxidative desulfurization (ODS) of dibenzothiophene as a model sulfur compound. The activity was compared with titanium supported-CMK-3. Structural and textural characterization of the catalysts was performed by means of N2 adsorption, XRD, UV–vis–DRS, Raman spectroscopy, XPS, TEM and TPR. The dispersion and the nature of the vanadium species depend on the V loading, so does the catalyst activity. Vanadium supported-CMK-3 with 7 wt.% of vanadium loading was the most active catalyst for ODS of DBT using hydrogen peroxide (H2O2) as oxidant and acetonitrile as solvent. 100% of DBT elimination was attained at short time in mild conditions. Carbon ordered mesoporous CMK-3 with high surface area and high pore volume promotes a very good anchorage of metallic oxides in the carbons framework reaching high active sites distribution and more stable nanoclusters. The reusability of the catalyst indicates that V-CMK-3 is a potential catalyst for the ODS of dibenzothiophene.Fil: Rivoira, Lorena Paola. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación en Nanociencia y Nanotecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Juarez, Juliana. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación en Nanociencia y Nanotecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Falcon, Horacio. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación en Nanociencia y Nanotecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Gómez Costa, Marcos Bruno. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación en Nanociencia y Nanotecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Anunziata, Oscar Alfredo. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación en Nanociencia y Nanotecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Beltramone, Andrea Raquel. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación en Nanociencia y Nanotecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentin

Optimization of the synthesis of SBA-3 mesoporous materials by experimental design

SBA-3 mesoporous materials are characterized by hexagonal regular arrangements of channels with diameters >2 nm, high specific surface areas and high specific pore volumes. In the work reported herein, experimental design-response surface methodology (RSM) is used to model and optimize the synthesis conditions for SBA-3 mesoporous materials. In this study, we evaluate the influences of surfactant/silica source molar ratios, aging times, temperature and pH on the synthesis of SBA-3 mesoporous materials by analyzing the XRD intensities pertaining to the [100] signal. Response surfaces were obtained using theBoxeBehnken design, and the combination of reaction parameters was optimized. By applying statistical methodology, higher levels of the objective function (XRD intensities pertaining to the [100] signal) were obtained using cetyltrimethylammonium bromide (CTAB)/tetraethyl orthosilicate (TEOS) molar ratios of 0.07 and 0.16, HCl/TEOS molar ratios of 8 and 11, reaction temperatures of 35 and 45 C and aging times of 12e24 h. The mesoporous SBA-3 samples obtained were characterized using small-angle X-ray powder diffraction (XRD), BET, FTIR and 29Si NMR-MAS, scanning electron microscopy (SEM) andtransmission electron microscopy (TEM).Fil: Ponte, María Virginia. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación en Nanociencia y Nanotecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; ArgentinaFil: Rivoira, Lorena Paola. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación en Nanociencia y Nanotecnología; ArgentinaFil: Cussa, Jorgelina. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación en Nanociencia y Nanotecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; ArgentinaFil: Martinez, Maria Laura. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación en Nanociencia y Nanotecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; ArgentinaFil: Beltramone, Andrea Raquel. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación en Nanociencia y Nanotecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; ArgentinaFil: Anunziata, Oscar Alfredo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación en Nanociencia y Nanotecnología; Argentin

Experimental design optimization of the tetralin hydrogenation over Ir-Pt-SBA-15

Experiment design-response surface methodology (RSM) is used in this work to model and optimize two responses in the hydrogenation of tetralin to decalin using bimetallic Ir-Pt-SBA-15 catalyst. In this study, we analyze the influence of the nature of the catalyst (metal molar fraction and metal loading), the catalyst/substrate ratio and the temperature of the reaction as factors for the design. The responses analyzed were conversion at 3 h and at 5 h of reaction time. The response surfaces were obtained with the Box-Behnken design, finding the best combination between the reaction parameters that allowed optimizing the process. By applying the statistic methodology, the higher levels of the two objective functions were obtained employing the catalyst with 1 wt.% of iridium and 0.7-0.8 wt.% of platinum; the optimal ratio between mass of catalyst and mole of tetralin was 17-19 g/mol and temperature between 200 and 220 °C.Fil: Vallés, Verónica Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación en Nanociencia y Nanotecnología; ArgentinaFil: Ledesma, Brenda Cecilia Soledad. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación en Nanociencia y Nanotecnología; ArgentinaFil: Rivoira, Lorena Paola. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación en Nanociencia y Nanotecnología; ArgentinaFil: Cussa, Jorgelina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación en Nanociencia y Nanotecnología; ArgentinaFil: Anunziata, Oscar Alfredo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación en Nanociencia y Nanotecnología; ArgentinaFil: Beltramone, Andrea Raquel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina. Universidad Tecnológica Nacional. Facultad Regional Córdoba. Centro de Investigación en Nanociencia y Nanotecnología; Argentin