Catalytic activity of copper and palladium based catalysts for toluene total oxidation

In this study, catalysts containing 0.5 wt.% of palladium or 5 wt.% of copper were compared towards toluene total oxidation using FAU Zeolite and ZrO₂ supports. A 0.5%Pd/NaFAU and 5%Cu/ZrO₂ were found to be promising catalysts for this reaction. Palladium presented then a better affinity for FAU zeolite and copper oxide had a better affinity for zirconia. The performances of Pd based catalysts were correlated to interaction between the active phase and the support whereas the activity of copper oxide was related to oxygen mobility property of the support leading to copper oxide particles easily reducible. Support modifications, yttrium addition for ZrO₂ and cation exchange for the zeolite FAU, still enhanced the catalytic activity. Therefore, 0.5%Pd/CsFAU and 5%Cu/Zr₉₅Y₅ samples were found to be interesting catalysts for total VOC oxidation.     

Steam reforming of methanol over ruthenium impregnated ceria,alumina and ceria–alumina catalysts

The wet impregnation method was used to prepare different ruthenium promoted Ce–Al catalysts. These catalysts were used in the steam reforming of methanol reaction (SRM). The effects of the reaction temperature (200–400 C) and the catalyst composition were studied for optimization reasons. The steam to methanol molar ratio was kept constant (S/M = 2). The promotion of cerium/aluminum oxides with Ru enhanced their catalytic activity. The catalytic test results showed that the Ru/Ce combination was the most beneficial. The synergy between Ru and cerium oxide led to the formation of active sites with excellent redox properties. For high active phase content, the 5 RuCe catalyst exhibited the highest hydrogen production amount with no CO formation. This catalyst was kept under stream for 5 days at 400 C, and no significant deactivation was observed. Copyright © 2016 John Wiley & Sons, Ltd.     

Promotional effect of gold added to palladium supported on a new mesoporous TiO2 for total oxidation of volatile organic compounds

Gold and palladium were supported on a mesoporous TiO₂ for total oxidation of volatile organic compounds (VOCs). Mesoporous high surface area titania support was synthesised using of Ti(OC₂H₅)₂ in the presence of CTMABr surfactant. After removing the surfactant molecules, 0.5 or 1.5 wt% of palladium and 1 wt% of gold were precipitated on the support by, respectively, wet impregnation and deposition–precipitation methods. The activity for toluene and propene total oxidation of the prereduced samples follows the same order: 0.5%Pd-1%Au/TiO₂ > 1.5%Pd/TiO₂ > 0.5%Pd/TiO₂ > 1%Au-0.5%Pd/TiO₂ > 1%Au/TiO₂ > TiO₂. Moreover, a catalytic comparison with samples based on a conventional TiO₂, shows the catalytic advantage of the mesoporous TiO₂ support. The promotional effect of gold added to palladium could be partly explained by small metallic particles (TEM), but meanly by metallic particles made up of Au-rich core with a Pd-rich shell. Moreover, the hydrogen TPR profile of 0.5%Pd-1%Au/TiO₂ shows only the signal attributed to small PdO particles. Gold also implies a protecting effect of the support under reduction atmosphere. Operando diffuse reflectance infrared fourier transform (DRIFT) spectroscopy was carried on and allowed to follow the VOCs oxidation and the formation of coke molecules, but also a metallic electrodonor effect to the adsorbed molecule which increases in the same order as the activity for oxidation reaction. The presence of coke after test was also shown by DTA–TGA by exothermic signals between 300 and 500 °C and by EPR (g = 2.003).     

Band-edge phenomena and spontaneous polarisation above and below Tc FOR BaTiO3 and KNbO3

The band-edge phenomena and the polarisation induced effects are analysed through the Bloch orbital interactions above and below T_c.     

Ni based catalysts promoted with cerium used in the steam reforming of toluene for hydrogen production

Ni_xMg_6?xAl_1.8Ce_0.2 (with 0 ≤ x ≤ 6) mixed oxides catalysts were prepared by hydrotalcite route. All the oxides were calcined at 800 °C and characterized by different physico-chemical methods. The catalysts are then reduced before their use in the steam reforming of toluene. The XRD and TG/DTA confirmed the formation of the hydrotalcite structure for the non-calcined samples. The N₂ adsorption/desorption results revealed that all catalysts correspond to mesoporous materials. The study by temperature programmed reduction (H₂-TPR) showed that the reducibility of the catalysts is influenced by the nickel content. The CO₂-TPD results showed that the catalyst with high magnesium content present the highest basicity. The Ni₂Mg₄Al_1.8Ce_0.2 shows the best toluene conversion among all the catalysts and it was then compared to a non-promoted catalyst. The spent catalysts were characterized by TPO, TG/DTA and XRD and they didn't reveal any coke formation.     

Syngas production by the CO2 reforming of CH4 over Ni–Co–Mg–Al catalysts obtained from hydrotalcite precursors

The catalytic performance of the Ni, Co, Mg, and Al mixed-oxide solids, synthesized via hydrotalcite route, was investigated towards the dry reforming of methane for hydrogen production. The hydrotalcite structure was successfully obtained upon the synthesis. After calcination at 800 °C under an air flow, this structure was completely decomposed and the resulting oxides (Co_xNi_yMg_zAl₂800, x and y = 0; 1; 2; 3; 4, z = 2; 4, x + y + z = 6, x, y, and z are the molar ratios) were used as catalysts and were characterized using X-ray diffraction and Temperature-Programmed Reduction. The dry reforming of methane was carried out using a mixture of CH₄:CO₂ (1:1) after 2 h of reduction under an H₂ flow at 800 °C. Co₂Ni₂Mg₂Al₂800 showed the highest catalytic activity in the studied series, ascribable to an interaction between Ni and Co, which is optimal for such Co/Ni ratio. The post-reaction characterization of the catalytic samples by X-ray diffraction and Differential Scanning Calorimetry evidenced a better resistance towards carbon deposition for the catalysts where Co molar ratio is higher than Ni.     

Enzymic browning in apricots (Prunus armeniaca)

Enzymic browning in apricots (Prunus armeniaca L) was found to be catalysed by a catechol oxidase (o-diphenol oxidase) and a laccase (p-diphenol oxidase), both acting on catechin and chlorogenic acid as the natural substrates. The laccase was identified as such by substrate specificity tests and the effects of selective inhibitors. The enzymes were tightly bound to the fruit tissue and were inactivated by holding at 80°C for 10 min. The levels of phenolic compounds in healthy and rotted apricot tissue were compared by paper chromatography; the levels of catechin and chlorogenic acid were reduced in the rotted tissue.     

Specificity of practice: Interaction between concurrent sensory information and terminal feedback.

In 2 experiments, the authors investigated a potential interaction involving the processing of concurrent feedback using design features from the specificity of practice literature and the processing of terminal feedback using a manipulation from the guidance hypothesis literature. In Experiment 1, participants produced (198 trials) flexion-extension movements to reproduce a specific pattern of displacement over time with or without vision of the limb position and with 100% or 33% knowledge of results (KR) frequency. The transfer test was performed without vision and KR. In Experiment 2, the authors assessed whether sensory information processing was modulated by the amount of practice. Participants performed 54 or 396 trials under a 100% or a 33% KR frequency with vision before being transferred to a no-vision condition without KR. Results of both experiments indicated that the Vision-33% condition suffered a larger detrimental effect of withdrawing visual information than the Vision-100% condition. Experiment 2 indicated that this detrimental effect increased with practice. These results indicated the reduction in terminal feedback prompted participants to more deeply process the concurrent visual information thus reinforcing their dependency on the visual information. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Influence of the exchanged cation in Pd/BEA and Pd/FAU zeolites for catalytic oxidation of VOCs

0.5 wt% palladium supported on exchanged BEA and FAU zeolites were prepared, characterized and tested in the total oxidation of volatile organic compounds (VOCs). The BEA and FAU zeolites were exchanged with different cations to study the influence of alkali metal cations (Na⁺, Cs⁺) and H⁺ in Pd-based catalysts on propene and toluene total oxidation. The exchange with different cations (Na⁺, Cs⁺) and H⁺ led to a decrease of the surface area and the micropore volume. All Pd/BEA and Pd/FAU zeolites were found to be powerful catalysts for the total oxidation of VOCs. They were active at low temperature and totally selective for CO₂ and H₂O. However, their activity depends significantly on the type of zeolite and on the nature of the charge-compensating cation. The activity order for propene and toluene oxidation on FAU catalysts, Pd/CsFAU > Pd/NaFAU > Pd/HFAU, is the reverse of the activity order on BEA catalysts: Pd/HBEA > Pd/NaBEA > Pd/CsBEA. The catalytic activities can be rationalized in terms of the influence of the electronegativity of the charge-compensating cation on the Pd particles, the Pd dispersion, the PdO reducibility and the adsorption energies for VOCs.