Preparation of Pt catalysts supported on activated carbon felts (ACF)

Activated carbon felts (ACFs) have been used as supports for Pt catalysts. The preparation was carried out by the impregnation method using chloroplatinic acid as metal precursor. The effect of impregnation time and surface chemistry of the support on the catalytic properties and the characteristics of the metallic phase have been investigated. Nitrobenzene (Nbz) hydrogenation in liquid phase at 25 °C and cyclohexane (CH) dehydrogenation in gas phase at 300 °C were used as catalytic tests. The state of platinum in reduced catalysts (at 100 and 350 °C) was studied by TPR and XPS. Oxygen surface groups only produce a slight effect on the catalytic properties. The use of low impregnation times (30 min) during the preparation of Pt/ACF leads to catalysts with Pt mainly deposited in the outer shell of the fibers, while at higher impregnation times, the metallic atoms seem to be deposited inside the pores. Pt(0) species appear in catalysts reduced at 100 °C by effect of the reducing properties of the carbon fiber exhibiting a considerable catalytic activity for Nbz hydrogenation.Fil: de Miguel, Sergio Ruben. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; ArgentinaFil: Vilella, Irene María Julieta. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; ArgentinaFil: Jablonski, Estanislao Lorenzo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; ArgentinaFil: Scelza, Osvaldo Antonio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; ArgentinaFil: Salinas Martinez de Lecea, C.. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; ArgentinaFil: Linares Solano, A.. Universidad de Alicante; Españ

MgAl2O4 spinel prepared by novel mechanochemical synthesis used as a support of multimetallic catalysts for paraffin dehydrogenation

The catalytic performance in nbutane dehydrogenation of bimetallic PtSn, PtGa and PtIn, and tri metallic PtSnIn and PtSnGa catalysts (with low metal contents) supported on a MgAl2O4 prepared by a novel mechanochemical synthesis was evaluated both in flow and pulse equipment. The influence of the addition of different promoters (Sn, Ga and In) to Pt on the activity, selectivity and deactivation in the nbutane dehydro genation reaction was studied. Stability experiments through successive reactionregeneration cycles were car ried out for selected catalysts. In order to correlate the properties of the metallic phase of the catalysts with the catalytic behavior, several characterization techniques were used, such as test reactions of the metallic phase (cyclohexane dehydrogenation and cyclopentane hydrogenolysis), TPR, XPS, H2 chemisorption and TEM. Bimetallic PtSn catalyst has a better catalytic behavior than PtIn and PtGa ones. For PtSnM (M: In or Ga) cat alysts, whereas Ga addition to the bimetallic catalyst does not practically modify the dehydrogenation perform ance, the addition of In produces an increase of the activity and the selectivity to butenes. Characterization results indicate the presence of geometric effects for the PtSn catalyst, and geometric and electronic effects for PtIn and PtGa ones. For trimetallic catalysts, the presence of a close contact between Pt, Sn and In or Ga in both trimetallic catalysts was found, mainly due to geometric effects like blocking and dilution of the active sites by the promoters. In stability experiments, the trimetallic PtSnIn/MgAl2O4 catalyst clearly displays the best cat alytic performance along reactionregeneration cycles, though PtSnGa and PtSn catalysts also showed a very good behavior through the successive cycles. The characterization of these catalysts after cycles shows that their metallic phases are slightly modified along the cycles.Fil: Bocanegra, Sonia Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones En Catalisis y Petroquímica "ing. Jose Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones En Catalisis y Petroquímica "ing. Jose Miguel Parera"; ArgentinaFil: Guerrero Ruiz, A.. Universidad Nacional de Educación a distancia. Facultad de Ciencias. Departamento de Química Inorgánica y Química Técnica; EspañaFil: Scelza, Osvaldo Antonio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones En Catalisis y Petroquímica "ing. Jose Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones En Catalisis y Petroquímica "ing. Jose Miguel Parera"; ArgentinaFil: de Miguel, Sergio Ruben. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones En Catalisis y Petroquímica "ing. Jose Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones En Catalisis y Petroquímica "ing. Jose Miguel Parera"; Argentin

Performance of PtSn catalysts supported on MAl2O4 (M: Mg or Zn) in n-butane dehydrogenation: characterization of the metallic phase.

The Sn(0.3 or 0.5 wt.%) addition to Pt(0.3 wt.%)/ZnAl2O4 and Pt(0.3 wt.%)/MgAl2O4 catalysts leads to an increase of the activity and selectivity to olefins in the n-butane dehydrogenation reaction. Slight differences in the catalytic behaviour were found between 0.3 and 0.5 wt.% of Sn added to Pt in both catalyst series. Besides, the bimetallic catalysts also show a good stability through the five successive reaction-regeneration cycles, mainly the PtSn/MgAl2O4 one. The mono- and bimetallic catalysts were characterized by using different techniques: tests reactions of the metallic phase (cyclohexane dehydrogenation and cyclopentane hydrogenolysis), temperature programmed reduction, X-ray photoelectron spectroscopy, H2 chemisorption, microcalorimetric measurements of the propylene adsorption and XRD. Results show that the nature of the metallic phase in monometallic samples appears to be different for the two supports. Thus, metallic particles with a very low concentration of hydrogenolytic sites (steps, corners and edges) would exist in the Pt/ZnAl2O4 catalyst in contrast with the structure of the metallic phase of the Pt/MgAl2O4 one, where the existence of an important concentration of hydrogenolytic sites is clearly observed (according to the cyclopentane hydrogenolysis results). The modification of Pt by the Sn addition clearly improves the catalytic behaviour in n-butane dehydrogenation due to important changes in the structure of the metallic phase. Thus, when Sn is added to Pt/ZnAl2O4 and Pt/MgAl2O4 catalysts the metallic surface structure seems to be more complex. In fact, results would indicate not only a partial formation of PtSn alloys or intermetallic compounds between Pt0 and a fraction of Sn(0), but also a surface enrichment in Sn, dilution effects as well as the presence of tin stabilized on the support, probably as Sn(II/IV) oxides and SnCl2 species.Fil: Bocanegra, Sonia Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Guerrero-Ruiz, A.. Universidad Nacional de Educación a Distancia; EspañaFil: de Miguel, Sergio Ruben. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Scelza, Osvaldo Antonio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentin

Development of PtGe and PtIn anodic catalysts supported on carbonaceous materials for DMFC

Bimetallic PtGe and PtIn catalysts (Ge/Pt and In/Pt molar ratios = 0.33, 17 wt.% Pt loading) were prepared over carbonaceous supports (carbon Vulcan, carbon nanotubes and structured mesoporous carbon). The liquid phase deposition–reduction method by using 0.4 M sodium borohydride as a reducing agent was employed. The electrocatalytic activity for methanol oxidation was compared with a commercial Pt/CV E-TEK catalyst. The onset potential of the CO oxidation was shifted to less positive values for carbon Vulcan and carbon nanotubes supported catalysts and with a smaller effect in the case of mesoporous carbon supported ones. The best electrocatalytic performance was obtained by using carbon Vulcan as support of bimetallic catalysts, followed by carbon nanotubes. The performance of mesoporous carbon as a support was not adequate. PtGe/CV, PtGe/NT and PtIn/CV catalysts displayed the best performance in DMFC. The good performance of these catalysts could be due to the presence of small particle sizes with a narrow distribution, and to geometric effects (observed from different characterization techniques) related to a probable decoration of Ge or In around the small Pt particles.Fil: Veizaga, Natalia Soledad. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; ArgentinaFil: Paganin, Valdecir A.. Universidade de Sao Paulo; BrasilFil: Rocha, Thairo A.. Universidade de Sao Paulo; BrasilFil: Scelza, Osvaldo Antonio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; ArgentinaFil: de Miguel, Sergio Ruben. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; ArgentinaFil: Gonzalez, Ernesto R.. Universidade de Sao Paulo; Brasi

Promoting Effect of Tin in Platinum Electrocatalysts for Direct Methanol Fuel Cells (DMFC)

Pt-Sn anodic catalysts supported on multiwall carbon nanotubes, mesoporous carbon and Vulcan carbon were prepared using a deposition-reduction technique with sodium borohydride, characterized by different techniques and tested as anodes in a single direct methanol fuel cell at low temperatures. Characterization and CO stripping results indicate the presence of promoting effects of Sn over Pt in catalysts supported on Vulcan carbon and carbon nanotubes. This would mainly be caused both by geometric modifications induced by Sn placed in the surroundings of the active metal phase and probable electronic effects. These promoting effects make the oxidation of CO to CO2 at low potentials easier, thus improving the CO tolerance of the anodic electrocatalyst. On the other hand, Pt-Sn catalysts supported on mesoporous carbon do not show a proper metallic phase needed for a good electrochemical behavior. When catalysts were tested in a DMFC, Pt-Sn catalysts supported on Vulcan carbon and carbon nanotubes gave a better power density than a commercial one mainly when working at low current densities.Fil: Veizaga, Natalia Soledad. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; ArgentinaFil: Rodriguez, Virginia Ines. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; ArgentinaFil: Rocha, Thairo A.. Universidade de Sao Paulo; BrasilFil: Bruno, Mariano Martín. Comisión Nacional de Energía Atómica. Gerencia Química. CAC; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Scelza, Osvaldo Antonio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; ArgentinaFil: de Miguel, Sergio Ruben. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; ArgentinaFil: Gonzalez, Ernesto R.. Universidade de Sao Paulo; Brasi