Mn-based oxide supports were synthesized using different procedures: (i) carbonate co-precipitation method, leading to the formation of a hexaaluminate crystallized solid (La(0.2)Sr(0.3)Ba(0.5)MnAl(11)O(19)) and (ii) solid-solid diffusion method, leading to the formation of a doped theta-Al(2)O(3) crystallized solid (nominal composition: 60 wt% La(0.2)Sr(0.3)Ba(0.5)MnAl(11)O(19) + 40 wt% Al(2)O(3)). Impregnation of 1.0 wt%Pd was carried out on both oxides. The solids were tested for the catalytic methane combustion up to 700 degrees C. It was observed that adding palladium resulted in an important increase in the catalytic activity. The combined use of H(2)-TPR and XPS techniques reveals that only Mn(3+)/Mn(2+) redox "couple" is present in the solids, whatever the synthesis procedure used. The fraction Mn(3+)/Mn is proportional to the total Mn content in the solid support, whatever the sample structure (hexaaluminate or doped theta-Al(2)O(3)) and its morphology (large crystals or aggregates of small particles, respectively). Pd impregnation and further calcination at 650 degrees C has no significant effect on the Mn(3+)/Mn fraction. However, some changes in Mn(3+) reduction profile are observed, depending on the solid structure. Indeed, palladium addition strongly affects the manganese reducibility with an important shift of the reduction process to lower temperatures (approximately 100 degrees C). On the basis of redox properties observed for the different catalysts, a Mars-van-Krevelen redox mechanism, with oxygen transfer from support oxides to palladium particles, is proposed to explain the difference in terms of catalytic conversion and stability with respect to a 1.0 wt%Pd/Al(2)O(3) reference sample.
Ce-doped SiO x N y films are deposited by magnetron reactive sputtering from a CeO 2 target under nitrogen reactive gas atmosphere. Visible photoluminescence measurements regarding the nitrogen gas flow reveal a large emission band centered at 450 nm for a sample deposited under a 2 sccm flow. A special attention is paid to the origin of such an emission at high nitrogen concentration. Different emitting centers are suggested in Ce doped SiO x N y films (e.g. band tails, CeO 2 , Ce clusters, Ce 3+ ions), with different activation scenarios to explain the luminescence. X-ray photoelectron spectroscopy (XPS) reveals the exclusive presence of Ce 3+ ions whatever the nitrogen or Ce concentrations, while transmission electron microscopy (TEM) shows no clusters or silicates upon high temperature annealing. With the help of photoluminescence excitation spectroscopy (PLE), a wide excitation range from 250 nm up to 400 nm is revealed and various excitations of Ce 3+ ions are proposed involving direct or indirect mechanisms. Nitrogen concentration plays an important role on Ce 3+ emission by modifying Ce surroundings, reducing the Si phase volume in SiO x N y and causing a nephelauxetic effect. Taking into account the optimized nitrogen growth parameters, the Ce concentration is analyzed as new parameter. Under UV excitation, a strong emission is visible to the naked eye with high Ce 3+ concentration (6 at. %). No saturation of the photoluminescence intensity is observed, confirming again the lack of Ce cluster or silicate phase formation due do the nitrogen presence.
A co-sputtered Pt x Pd y Al z ternary system was investigated for potential use as anode catalyst for the electrooxidation of aqueous sulphur dioxide (SO 2 ), a key reaction in the hybrid sulphur (HyS) process for splitting water into hydrogen and oxygen. Combining the noble metals Pt and Pd with Al resulted in no significant improvement in onset potential; however, current output was improved for the majority of the electrocatalysts evaluated. Of these electrocatalysts, only a single ternary composition exhibited improved stability when compared to pure Pt. It was found that a combination of Pt 40 Pd 57 Al 3 (annealed at 900°C) exhibited superior performance when compared to pure Pt and the previously determined best binary electrocatalyst, i.e. Pt 3 Pd 2 . Current density (mA.mg Pt −1 ) increased from 108.11 to 181.21 and finally to 396.73 for Pt, Pt 3 Pd 2 and Pt 40 Pd 57 Al 3 , respectively, indicating an increase in activity that correlates with a decrease in Pt content. Atomic force microscopy (AFM) revealed an increase in surface roughness for Pt, Pt 3 Pd 2 and Pt 40 Pd 57 Al 3 , while the occurrence of metal interaction and certain degrees of Al migration (a result of annealing) was confirmed for Pt 40 Pd 57 Al 3 by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction analysis (XRD).
KeyWordsColumn liquid chromatography Synthesis of bonded stationary phases Organometallic complexes Charge-transfer interactions PAHs
SummaryThe preparation, characterization and potential liquid chromatographic applications of various organometallic iron complexes silica stationary phases are presented. These new supports are synthesized by covalently linking ferrocene, as well as some of its cationic derivatives, to appropriately derivatized silica support matrices. These columns exhibit moderate to high selectivity towards the separation of polycyclic aromatic hydrocarbons (PAHs). A charge transfer retention mechanism has been proposed. A comparison with a reference stationary phase, 3,5-dinitrobenzamide (DNB), to quantify the acceptor power of the new stationary bonded phases, is also reported. Finally the effect of varying the derivatives of the bonded metallocene on PAHs retention is discussed.
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