Exchange and oxidation of CO on O-predosed Rh---Al2O3 and Rh---CeO2 catalysts

Exchange and oxidation of C¹⁶O were investigated at 450°C on ¹⁸O-predosed Rh and Pt catalysts supported on A1₂O₃, CeO₂ and CeO₂-Al₂O₃. In all cases, a rapid exchange of C¹⁶O with the surface can be observed. CO oxidation leads to C¹⁶O₂, C¹⁶O¹⁸O and C¹⁸O₂. Significant formation of C¹⁶O₂ is due to the relatively high ¹⁶O coverage in reaction resulting from the C¹⁶O exchange and from an exchange between O surface species and ¹⁶O internal atoms. Hydrogen is also formed via a water-gas shift reaction (CO + surface OH) in higher proportion on CeO₂-containing catalysts than on A1₂O₃. Chlorine inhibits all the reactions (exchange, oxidation and WGS) and particularly the internal exchange.     

Reactivity of steam in exhaust gas catalysis III. Steam and oxygen/steam conversions of propane on a Pd/Al2O3 catalyst

A 1% Pd catalyst (38% dispersion) was prepared by impregnating a γ-alumina with palladium acetylacetonate dissolved in acetone. The behaviour of this catalyst in oxidation and steam reforming (SR) of propane was investigated. Temperature-programmed reactions of C₃H₈ with O₂ or with O₂ + H₂O were carried out with different stoichiometric ratios S(S =[O₂]/5[C₃H₈]). The conversion profiles of C₃H₈ for the reaction carried out in substoichiometry of O₂ (S < 1) showed two discrete domains of conversion: oxidation at temperatures below 350°C and SR at temperatures above 350°C. The presence of steam in the inlet gases is not necessary for SR to occur: there is sufficient water produced in the oxidation to form H₂ and carbon oxides by this reaction. Contrary to what was observed with Pt, an apparent deactivation between 310 and 385°C could be observed with Pd in oxidation. This is due to a reduction of PdO_x into Pd⁰, which is much less active than the oxide in propane oxidation. Steam added to the reactants inhibits oxidation while it prevents the reduction of PdO_x into Pd⁰. Compared to Pt and to Rh, Pd has a higher thermal resistance: no deactivation occurred after treatment up to 700°C and limited deactivation after treatment up to 900°C, provided that the catalyst is maintained in an oxygen-rich atmosphere during the cooling.     

Accelerated sintering of PtRh/Al2O3 catalysts in an oxygen periodic pulse flow

PtRh catalysts were prepared by coimpregnation, with chlorine-free precursors of a -alumina. They were sintered at 973 K under a continuous flow of O₂ (1% in Ar or air) or of a flow of Ar into which pulses of O₂ were injected periodically. Under the latter conditions the sintering was significantly accelerated, particularly for a certain value of the period of O₂ pulses.     

Enthalpy recovery of gases issued from H2 production processes: Activity and stability of oxide and noble metal catalysts in oxidation reaction under highly severe conditions

Oxidation activity and stability under reaction was investigated for a series of mixed oxide catalysts, doped or not by a precious metal (Pd, Pt). The reaction feedstock, containing CO, H₂, CH₄, CO₂ and H₂O, simulated gases issued from H₂ production processes for fuel cells. Contrarily to conventional noble metal catalysts, mixed oxide samples present generally good stability under reaction at high temperature. The activities measured for the perovskite and hexaaluminate catalysts, are however largely lower than that of the reference Pd/Al₂O₃ catalyst. High activities were obtained after impregnation of 1.1 wt.% Pd or 0.8 wt.% Pt on the hexaaluminates samples. Even if Pd/Al₂O₃ was found to present a high activity, this sample suffered from drastic deactivation at 700 °C. Better stability were obtained on perovskite. Furthermore, doping hexaaluminate by Pt led to samples with good activities and high stability. Even if better activities were obtained by doping the hexaaluminate samples by Pd, the Pd/BaAl₁₂O₁₉ strongly deactivated, as it was previously observed for the reference catalyst. Interestingly, this Pd deactivation was not observed when Pd was impregnated on the Mn substituted hexaaluminate, leading to a stable and active catalyst. This suggests that it is possible to stabilize the palladium in its oxidized form at high temperature (700 °C) on the surface of some supports.     

Characterisation by TPR, XRD and NOx Storage Capacity Measurements of the Ageing by Thermal Treatment and SO2 Poisoning of a Pt/Ba/Al NOx-Trap Model Catalyst

The deactivation of a Pt/Ba/Al₂O₃ NO _x -trap model catalyst submitted to SO₂ treatment and/or thermal ageing at 800 °C was studied by H₂ temperature programmed reduction (TPR), X-ray diffraction (XRD) and NO _x storage capacity measurements.The X-ray diffractogram of the fresh sample exhibits peaks characteristic for barium carbonate. Thermal ageing leads to the decomposition of barium carbonate and to the formation of BaAl₂O₄. The TPR profile of the sulphated sample shows the presence of (i) surface aluminium sulphates, (ii) surface barium sulphates, (iii) bulk barium sulphates. The exposure to SO₂ after ageing leads to a small decrease of the surface barium-based sulphates, expected mainly as aluminate barium sulphates. This evolution can be attributed to a sintering of the storage material. TPR experiments also show that thermal treatment at 800 °C after the exposure to SO₂ involves the decomposition of aluminium surface sulphates to give mainly bulk barium sulphates, also pointed out by XRD. Thus, the thermal treatment at 800 °C leads to a stabilization of the sulphates.These results are in accordance with the NO _x storage capacity measurements. On non-sulphated catalysts, the treatment at 800 °C induces to a decrease of the NO _x storage capacity, showing that barium aluminate presents a lower NO _x storage capacity than barium carbonate. Sulphation strongly decreases the NO _x storage capacity of catalysts, whatever the initial thermal treatment, showing that barium sulphates inhibit the NO₂ adsorption. Moreover, the platinum activity for the NO to NO₂ oxidation is lowered by thermal treatments.     

The effects of hydrogen pressure and temperature on the methylcyclopentane conversion on Rh catalysts

The effect of hydrogen pressure (pH₂) and temperature (T) was investigated on the hydrogenolytic ring opening of methylcyclopentane (MCP) over silica and alumina supported rhodium catalysts. Strong dependence could be seen in the activity and in distribution of ring opening products as a function of reaction conditions. Temperature and hydrogen pressure did not affect the position of the first C–C bond rupture. However, the final ring opening product distribution was largely influenced by the reaction conditions due to the different ability of intermediates to undergo further hydrogenolysis.     

Oxygen Storage and Mobility on Model Three-Way Catalysts

Oxygen storage capacity (OSC) of TW catalysts has a strong impact on their performances under oscillatory conditions. This paper reviews the different methods developed for OSC measurements, the effects of catalyst composition on OSC as well as the impact of OSC on TW catalysis, concentrating on the results obtained in our laboratory. Use of OSC measurements for catalysts control (on-board diagnostic) is also examined. The role of superoxide species as intermediates in the oxygen storage process will be emphasized. Finally, we shall review the recent developments on CeZr-based oxides.     

Influence of central command and ergoreceptors on the splanchnic circulation during isometric exercise

The splanchnic circulation can make a major contribution to blood flow changes. However, the role of the splanchnic circulation in the reflex adjustments to the blood pressure increased during isometric exercise is not well documented. The central command and the muscle chemoreflex are the two major mechanisms involved in the blood pressure response to isometric exercise. This study aimed to examine the behaviour of the superior mesenteric artery during isometric handgrip (IHG) at 30% maximal voluntary contraction (MVC). The pulsatility index (PI) of the blood velocity waveform of the superior mesenteric artery was taken as the study parameter. A total of ten healthy subjects [mean age, 21.1 (SEM 0.3) years] performed an IHG at 30% MVC for 90 s. At 5 s prior to the end of the exercise, muscle circulation was arrested for 90 s to study the effect of the muscle chemoreflex (post exercise arterial occlusion, PEAO). The IHG at 30% MVC caused a decrease in superior mesenteric artery PI, from 4.84 (SEM 1.57) at control level to 3.90 (SEM 1.07) (P = 0.015). The PI further decreased to 3.17 (SEM 0.70) (P = 0.01) during PEAO. Our results indicated that ergoreceptors may be involved in the superior mesenteric artery vasodilatation during isometric exercise.     

Characterisation and application of new carboxylic acid-functionalised ruthenium complexes as dye-sensitisers for solar cells

A series of ruthenium complexes with and without TiO₂ anchoring carboxylic acid groups have been synthesised and characterised using nuclear magnetic resonance (NMR), UV–vis and luminescence. These complexes were adsorbed on thin films of the wide band-gap semiconductor anatase and were tested as photosensitisers under standard conditions. I/V characteristics of such devices revealed superior performance of the non-symmetric complexes [4′-(4-bromophenyl)-[2,2′; 6′,2″] terpyridine]Ru(II) [4′-(4-bromophenyl)-[2,2′; 6′,2″] terpyridine-4,4″-dicarboxylic acid] and [2,2′; 6′,2″] terpyridine Ru(II) [2,2′; 6′,2″] terpyridine-4′-carboxylic acid with a maximum output power 0.016 mW cm⁻² under illumination at 100 mW cm⁻² AM1.5 and efficiencies 3 times higher than the symmetric complexes.     

Study of the oxygen diffusion on three-way catalysts: a kinetic model

Topics in Catalysis - A computer model was developed to take into account all the phenomena that can occur in 18O/16O isotopic exchange over Pt/CeZrO x materials: adsorption/desorption on the...