Phase stability and thermophysical properties of neodymium cerium composite oxide

Nd2CexO3+2x (x = 2.25, 2.5, 2.75, 3.0) were synthesized by solid-state reaction, and their phase stabilities and thermophysical properties were investigated. The X-ray diffraction (XRD) results indicated that Nd2CexO3+2x with fluorite structure were stable after long-term annealing at 1673 K. They have higher thermal expansion coefficients (TECs) than yttria-stabilized zirconia (YSZ) which is the typical thermal barrier coating (TBC) material, especially the thermal expansion as a function of temperature is parallel to that of the nickel-based superalloy.

Ethanol electrooxidation on Pt/C catalysts promoted with praseodymium oxide nanorods

The Pt/C electrocatalysts containing Pr6O11 nanorods were successfully prepared. By various electrochemical characterization methods, it was demonstrated that the Pr6O11 nanorods have an obviously promotive role for ethanol electrooxidation catalyzed by Pt/C. However, according to the stripping experiment, the promotive effect of Pr6O11 does not result from the easier electrooxidation of the intermediate adsorbate on Pt-Pr6O11/C than on Pt/C. It was supposed that Pr6O11 could promote a certain step in ethanol oxidation, and that the special morphology of the nanorods could further enhance the activity compared with nanoparticles.

Thermal barrier coating of lanthanum-zirconium-cerium composite oxide made by electron beam-physical vapor deposition

Lanthanum-zirconium-cerium composite oxide (La-2(Zr0.7Ce0.3)(2)O-7, LZ7C3) as a candidate material for thermal barrier coatings (TBCs) was prepared by electron beam-physical vapor deposition (EB-PVD). The composition, crystal structure, thermophysical properties, surface and cross-sectional morphologies and cyclic oxidation behavior of the LZ7C3 coating were studied. The results indicated that LZ7C3 has a high phase stability between 298 K and 1573 K, and its linear thermal expansion coefficient (TEC) is similar to that of zirconia containing 8 wt% yttria (8YSZ). The thermal conductivity of LZ7C3 is 0.87 W m(-1) K-1 at 1273 K, which is almost 60% lower than that of 8YSZ. The deviation of coating composition from the ingot can be overcome by the addition of excess CeO2 and ZrO2 during ingot preparation or by adjusting the process parameters.

Preparation, structure and oxide ion conductivity in Ce6-xYxMoO15-delta (x=0.1-1.4) solid solutions

The Ce6-xYxMoO15-delta solid solution with fluorite-related structure have been characterized by differential thermal analysis/thermogravimetry (DTA/TG), X-ray diffraction (XRD), IR, Raman, scanning electric microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) methods. The electric conductivity of samples is investigated by Ac impedance spectroscopy. An essentially pure oxide-ion conductivity of the oxygen-deficiency was observed in pure argon, oxygen and air. The highest oxygen-ion conductivity was found in Ce5.5Y0.5MoO15-delta ranging from 5.9 X 10(-5)(S cm(-1)) at 300 degrees C to 1.3 X 10(-2)(S cm(-1)) at 650 degrees C, respectively. The oxide-ion conductivities remained stable over 80 h-long test at 800 degrees C. These properties suggested that significant oxide-ionic conductivity exists in these materials at moderately elevated temperatures.

Partial oxidation of ethane to syngas over nickel-based catalysts modified by alkali metal oxide and rare earth metal oxide

The catalytic activity, thermal stability and carbon deposition of various modified NiO/gamma-Al2O3 and unmodified NiO/gamma-Al2O3 catalysts were investigated with a flow reactor, XRD, TG and UVRRS analysis. The activity and selectivity of the NiO/gamma-Al2O3 catalyst showed little difference from those of the modified nickel-based catalysts. However, modification with alkali metal oxide (Li, Na, K) and rare earth metal oxide (La, Ce, Y, Sm) can improve the thermal stability of the NiO/gamma-Al2O3 and enhance its ability to suppress carbon deposition during the partial oxidation of ethane (POE). The carbon deposition contains graphite-like species that were detected by UVRRS. The nickel-based catalysts modified by alkali metal oxide and rare earth metal oxide have excellent catalytic activities (C2H6 conversion of similar to 100%, CO selectivity of similar to 94%, 7x 10(4) l/(kg h), 1123 K), good thermal stability and carbon-deposition resistance.

A review of the selective reduction of NOx, with hydrocarbons under lean-burn conditions with non-zeolitic oxide and platinum group metal catalysts

Research on the selective reduction of NOx with hydrocarbons under lean-burn conditions using non-zeolitic oxides and platinum group metal (PGM) catalysts has been critically reviewed. Alumina and silver-promoted alumina catalysts have been described in detail with particular emphasis on an analysis of the various reaction mechanisms that have been put forward in the literature. The influence of the nature of the reducing agent, and the preparation and structure of the catalysts have also been discussed and rationalised for several other oxide systems. It is concluded for non-zeolitic oxides that species that are strongly adsorbed on the surface, such as nitrates/nitrites and acetates, could be key intermediates in the formation of various reduced and oxidised species of nitrogen, the further reaction of which leads eventually to the formation of molecular nitrogen. For the platinum group metal catalysts, the different mechanisms that have been proposed in the literature have been critically assessed. It is concluded that although there is indirect, mainly spectroscopic, evidence for various reaction intermediates on the catalyst surface, it is difficult to confirm that any of these are involved in a critical mechanistic step because of a lack of a direct quantitative correlation between infrared and kinetic measurements. A simple mechanism which involves the dissociation of NO on a reduced metal surface to give N(ads) and O(ads), with subsequent desorption of N-2 and N2O and removal of O(ads) by the reductant can explain many of the results with the platinum group metal catalysts, although an additional contribution from organo-nitro-type species may contribute to the overall NOx reduction activity with these catalysts.

On the nature of the silver phases of Ag/Al2O3 catalysts for reactions involving nitric oxide

The nature of the silver phases of Ag/Al2O3 catalysts (prepared by silver nitrate impregnation followed by calcination) was investigated by X-ray diffractograms (XRD), transmission electron microscopy (TEM) and UV-VIS analyses and related to the activity of the corresponding materials for the oxidation of NO to NO2. The UV-VIS spectrum of the 1.2 wt.% Ag/Al2O3 exhibited essentially one band associated with Ag+ species and the NO2 yields measured over this material were negligible. A 10 wt.% Ag/Al2O3 material showed the presence of oxidic species of silver (as isolated Ag+ cations and silver aluminate), but the UV-VIS data also revealed the presence of some metallic silver. The activity for the NO oxidation to NO2 of this sample was moderate. The same 10% sample either reduced in H-2 or used for the C3H6-selective catalytic reduction (SCR) of NO showed a significantly larger proportion of silver metallic phases and these samples displayed a high activity for the formation of NO2. These data show that the structure and nature of the silver phases of Ag/Al2O3 catalysts can markedly change under reaction feed containing only a fraction of reducing agent (i.e. 500 ppm of propene) in net oxidizing conditions (2.5% O-2). The low activity for N-2 formation during the C3H6-SCR of NO (reported in an earlier study) over the high loading sample can. therefore, he related to the presence of metallic silver. which is yet a good catalyst for NO oxidation to NO2. The reverse observations apply for the oxide species observed over the low loading sample, which is a good SCR catalyst but do not oxidize NO to NO2. (C) 2002 Elsevier Science B.V. All rights reserved.

OXIDATION OF CHLORIDE TO CHLORINE BY CEIV IONS MEDIATED BY DIFFERENT RUIV AND IRIV OXIDE-BASED CATALYSTS

A number of different, characterised, supported and unsupported oxides of Ru(IV) and Ir(IV) have been tested for activity as a chlorine catalyst in the oxidation of brine by Ce(IV) ions. All the different materials tested gave yields of chlorine of > 90% and first-order kinetics for the reduction of the Ce(IV) ions. The samples prepared by the Adams method were the most active of the materials tested and are typified by high surface areas and appreciable activities per unit area. The kinetics of the catalysed reduction of Ce(IV) ions by brine were studied in detail using an Ru(IV) oxide prepared by the Adams method and supported on TiO2 and the results were rationalised in terms of an electrochemical model in which the rate-determining step is the diffusion-controlled reduction of Ce(IV) ions. In support of this model the measured activation energies for the oxidation of brine by Ce(IV) ions, catalysed by either a supported or unsupported Adams catalyst, were both close (18-21 kJ mol-1) to that expected for a diffusion-controlled reaction (ca. 15 kJ mol-1).

Selective Hydrogenation of alpha,beta-Unsaturated Aldehydes and Ketones using Novel Manganese Oxide and Platinum Supported on Manganese Oxide Octahedral Molecular Sieves as Catalysts

The selective hydrogenation of ,-unsaturated aldehydes and ketones has been studied using ketoisophorone and cinnamaldehyde as model substrates using manganese oxide octahedral molecular sieve (OMS-2) based catalysts. For the first time, OMS-2 has been shown to be an efficient and selective hydrogenation catalyst. High selectivities for either the CC or CO double bond at approximate to 100% conversion were achieved by using OMS-2 and platinum supported on OMS-2 catalysts. Density functional theory (DFT) calculations showed that the dissociation of H2 on OMS-2 was water assisted and occurred on the surface Mn of OMS-2(001) that had been modified by an adsorbed H2O molecule. The theoretically calculated activation barrier was in good agreement with the experimentally determined value for the hydrogenation reactions, indicating that H2 dissociation on OMS-2 is likely to be the rate-determining step. A significant increase in the rate of reaction was observed in the presence of Pt as a result of the enhancement of H2 dissociative adsorption and subsequent reaction on the Pt or spillover of the hydrogen to the OMS-2 support. The relative adsorption strengths of ketoisophorone and cinnamaldehyde on the OMS-2 support compared with the Pt were found to determine the product selectivity.

Selective Hydrogenation of Halogenated Arenes using porous Manganese Oxide (OMS-2) and Platinum supported OMS-2 Catalysts

Porous manganese oxide (OMS-2) and platinum supported on OMS-2 catalysts have been shown to facilitate the hydrogenation of the nitro group on chloronitrobenzene to give chloroaniline with no dehalogenation. Complete conversion was obtained within 2 h at 25 [degree]C and, although the rate of reaction increased with increasing temperature up to 100 [degree]C, the selectivity to chloroaniline remained at 99.0%. Use of Pd/OMS-2 or Pt/Al2O3 resulted in significant dechlorination even at 25 [degree]C and 2 bar hydrogen pressure giving selectivity to chloroaniline of 34.5% and 77.8%, respectively, at complete conversion. This demonstrates the potential of using platinum group metal free catalysts for the selective hydrogenation of halogenated aromatics. Two pathways were observed for the analogous nitrobenzene hydrogenation depending on the catalyst used. The hydrogenation of nitrobenzene was found to follow a direct pathway to aniline and nitrosobenzene over Pd/OMS-2 in contrast to the OMS and Pt/OMS-2 catalysts which resulted in formation of nitrosobenzene, azoxybenzene and azobenzene/hydrazobenzene intermediates before complete conversion to aniline. These results indicate that for the Pt/OMS-2 the hydrogenation proceeds predominantly over the support with the metal acting to dissociate the hydrogen. In the case of the Pd/OMS-2 both the hydrogenation and the hydrogen adsorption occur on the metal sites.

Surface science studies of strong metal-oxide interactions on model catalysts

The strong metal support interaction (SMSI) was first described in 1978 by Tauster [1-4]. The effect was observed as a severely negative effect on CO and H2 uptake on the catalyst after high temperature calcination under reducing conditions (heating above ~ 700 K) [1,2]. It also had a negative effect on the reaction rate for reactions, such as alkane hydrogenolysis [5,6]. It appeared that the effect occurred for catalysts comprised of reducible supports which were treated at elevated temperature in reducing conditions [2-4]. A classic support which has manifested this behaviour in many studies is TiO2. Over the years following the first discovery of SMSI it has been recognised that the effect is not always negative – for instance for the CO-H2 reaction for which it appears to have a positive effect [5,6]. Further it was noted that hydrogen reduction was not necessary to observe the effect of CO adsorption suppression, it also occurs by vacuum treatment [7], though it should be noted that vacuum treatment at elevated temperature is, in effect, a reducing environment.