Ceria-based oxides as supports for LaCoO3 perovskite; catalysts for total oxidation of VOC

Supported LaCoO₃ perovskites with 10 and 20 wt.% loading were obtained by wet impregnation of different Ce_1−xZr_xO₂ (x = 0–0.3) supports with a solution prepared from La and Co nitrates, and citric acid. Supports were also prepared using the “citrate method”. All materials were calcined at 700 °C for 6 h and investigated by N₂ adsorption at −196 °C, XRD and XPS. XRD patterns and XPS measurements evidenced the formation of a pure perovskite phase, preferentially accumulated at the outer surface. These materials were comparatively tested in benzene and toluene total oxidation in the temperature range 100–500 °C. All catalysts showed a lower T₅₀ than the corresponding Ce_1−xZr_xO₂ supports. Twenty weight percent LaCoO₃ catalysts presented lower T₅₀ than bulk LaCoO₃. In terms of reaction rates per mass unit of perovskite calculated at 300 °C, two facts should be noted (i) the activity order is more than 10 times higher for toluene and (ii) the reverse variation with the loading as a function of the reactant, a better activity being observed for low loadings in the case of benzene. For the same loading, the support composition influences drastically the oxidative abilities of LaCoO₃ by the surface area and the oxygen mobility.     

Supported Co-based perovskites as catalysts for total oxidation of methane

Supported LaCoO₃ perovskites with 2, 5, 10, 15, 20 and 30 wt.% loading were prepared by impregnation of a Ce_0.8Zr_0.2O₂ support (40 m² g⁻¹) with: (i) a solution of La and Co nitrates and (ii) a “citrate” solution, namely containing La and Co nitrates, and citric acid. All precursors were decomposed and calcined at 700 °C for 5 h. XRD investigations indicated the formation of a pure perovskite phase only if citrates were used. These materials were tested as catalysts for methane combustion in the temperature range 300–700 °C. All catalysts showed a lower T₅₀ (the temperature at which the conversion level of methane is 50%) than the Ce_0.8Zr_0.2O₂ support or non-supported LaCoO₃. The activity increased continuously with the perovskite loading. The samples prepared from citrates were slightly more active than from nitrates. This is due to a more homogeneous surface, as indicated by XPS measurements. The presence of a well-characterized perovskite phase (as opposed to highly dispersed elements) seems necessary for good activity. A higher reaction rate per perovskite weight is observed for low loadings when compared to bulk LaCoO₃, but the variation with perovskite loading presents a breakpoint, suggesting complex interactions in the catalysts or in the oxidation mechanism.

In spite of the experimental impossibility to evaluate the area developed by the supported perovskite, an approximative approach strongly suggests a synergy between the support and supported species.     

Studies of the activation process over Pd perovskite-type oxides used for catalytic oxidation of toluene

Calcined and reduced catalysts Pd/LaBO₃ (B = Co, Fe, Mn, Ni) were used for the total oxidation of toluene. Easiness of toluene destruction was found to follow the sequence based on the T₅₀ values (temperature at which 50% of toluene is converted): Pd/LaFeO₃ > Pd/LaMnO_3+δ > Pd/LaCoO₃ > Pd/LaNiO₃. In order to investigate the activation process (calcination and reduction) in detail, the reducibility of the samples was evaluated by H₂-TPR on the calcined catalysts. Additionally, characterization of the Pd/LaBO₃ (B = Co, Fe) surface was carried out by X-ray photoelectron spectroscopy (XPS) at each stage of the global process, namely after calcination, reduction and under catalytic reaction at either 150 or 200 °C for Pd/LaFeO₃ and either 200 or 250 °C for LaCoO₃. The different results showed that palladium oxidized entities were totally reduced after pre-reduction at 200 °C for 2 h (2 L/h, 1 °C/min). As LaFeO₃ was unaffected by such a treatment, for the other perovskites, the cations B are partially reduced as B³⁺ (B = Mn) or B²⁺ even to B⁰ (B = Co, Ni). In the reactive stream (0.1% toluene in air), Pd⁰ reoxidized partially, more rapidly over Co than Fe based catalysts, to give a Pd²⁺/Pd⁴⁺ and Pd⁰/Pd²⁺/Pd⁴⁺ surface redox states, respectively. Noticeably, reduced cobalt species are progressively oxidized on stream into Co³⁺ in a distorted environment. By contrast, only the lines characteristic of the initial perovskite lattice were detected by XRD studies on the used catalysts. The higher activity performance of Pd/LaFeO₃ for the total oxidation of toluene was attributed here to a low temperature of calcination and to a remarkable high stability of the perovskite lattice whatever the nature of the stream which allowed to keep a same palladium dispersion at the different stages of the process and to resist to the oxidizing experimental conditions. On the contrary, phase transformations for the other perovskite lattices along the process were believed to increase the palladium particle size responsible of a lower activity.     

Co from partial reduction of La(Co,Fe)O3 perovskites for Fischer–Tropsch synthesis

Small Co clusters (d<10 nm) supported over mixed La–Co–Fe perovskites were successfully synthesized. These catalysts were active for Fischer–Tropsch (FT). Depending on the Co to Fe ratios the mixed perovskite exhibited two different forms: the rhombohedral phase of LaCoO₃ is maintained for the mixed perovskite when x>0.5, the orthorhombic phase of LaFeO₃ is found for x<0.5. Interestingly only one of these structures is active for the FT reaction: the orthorhombic structure. This is most likely due to the capacity of this material to maintain its structure even with a high number of cation vacancies. These cations (mostly Co) were on purpose extracted and reduced. Magnetic measurements clearly showed their metallic nature. Rhombohedral Co–Fe mixed perovskites (x≥0.5) cannot be used as precursors for Fischer–Tropsch catalysts: their partial reduction only consists in a complete reduction of Co³⁺ into Co²⁺.

The partial reduction of orthorhombic perovskites (x<0.5) leads to active Fischer–Tropsch (FT) catalysts by formation of a metal phase well dispersed on a cation-deficient perovskite. The FT activity is related to the stability of the precursor perovskite. When initially calcined at 600 °C, a maximum of 8.6 wt.% of Co⁰ can be extracted from LaCo_0.40Fe_0.60O₃ (compared to only 2 wt.% after calcination at 750 °C). The catalyst is then composed of Co⁰ particles of 10 nm on a stable deficient perovskite LaCo_0.05³⁺Fe_0.60³⁺O_2.40. Catalytic tests showed that up to 70% in the molar selectivity for hydrocarbons was obtained at 250 °C, 40% of which was composed of the C₂–C₄ fraction.     

Catalytic oxidation of 1,2-dichlorobenzene over ABO3-type perovskites

Several ABO₃-type perovskite oxides (A = La, Y, Nd or Gd; B = Fe, Mn, Cr or Co) have been investigated as catalysts for the oxidation of 1,2-dichlorobenzene (o-DCB), a model compound for the highly toxic polychlorinated dibenzodioxins. Initial transient and steady state activity measurements were conducted with all catalysts in the absence and presence of water. Perovskites containing Cr in the B-site were more active than perovskites containing other transition metals, with YCrO₃ being the most active catalyst among the different systems studied. Furthermore, YCrO₃ did not show any loss of its initial activity after several hours on stream. Other perovskites lost 10–20% of their initial activity within the first 5–10 h on stream. This loss was associated with a corresponding loss in BET surface area. With the exception of LaCoO₃, all perovskites retained their crystalline structure upon exposure to o-DCB under reaction conditions. LaCoO₃ was converted to LaOCl and Co₃O₄. The presence of water appeared to enhance the catalytic activity of some perovskites. This effect can be attributed to a faster removal of Cl⁻ ions from the catalyst surface via their reaction with water.     

A comparison between hexaaluminates and perovskites for catalytic combustion applications

Hexaaluminates and perovskites are two promising candidates for use in catalytic combustion applications. In the present study two hexaaluminates, LaMnAl₁₁O₁₉ and LaCoAl₁₁O₁₉, were compared with two perovskites, LaMnO₃ and LaCoO₃, with respect to their thermal stability and catalytic activity for combustion of methane and gasified biomass. The results showed that the hexaaluminates retained a much higher surface area even after calcination at 1200 °C compared to the perovskites. LaMnAl₁₁O₁₉ showed the highest catalytic activity of all catalysts. LaCoAl₁₁O₁₉ generally showed low activity. Of the two perovskites, LaCoO₃ was the most active, and the initial test run the activity for biomass combustion were close to that one of LaMnAl₁₁O₁₉ even though its surface area was only one tenth of the hexaaluminate's. However, it was severely deactivated in the second test run. Similar deactivation but less severe was also found for the other catalyst.     

Preparation and characterization of inexpensive heterogeneous catalysts for air pollution control: Two case studies

Relatively inexpensive heterogeneous catalysts for two reactions of great importance in air pollution control, NO reduction and VOC combustion, were prepared and characterized. Apart from their common practical goal and the frequent need for simultaneous removal of air pollutants, these reactions share a similar redox mechanism, in which the formulation of more effective catalysts requires an enhancement of oxygen transfer.

For NO reduction, supported catalysts were prepared by adding a metal (Cu, Co, K) using ion exchange (IE) and incipient wetness impregnation (IWI) to chars obtained from pyrolysis of a subbituminous coal. The effects of pyrolysis temperature, between 550 and 1000 °C, on selected catalyst characteristics (e.g., BET surface area, XRD spectrum, support reactivity in O₂) are reported. For IE catalysts, the surface area increased in the presence of the metals while the opposite occurred for IWI catalysts. For the Co-IE catalysts, the highest surface area was obtained at 700 °C. The XRD results showed that, except for Cu (which exhibited sharp Cu⁰ peaks), the catalysts may be highly dispersed (or amorphous) on the carbon surface. For the C–O₂ reaction the order of (re)activity was K  Co > Cu for IE catalysts and K > Cu > Co for IWI catalysts. For NO reduction the orders were K > Co > Cu (IE catalysts) and Cu > Co > K (IWI catalysts). In all cases the catalytic (re)activity for NO reduction was lower than that exhibited for the C–O₂ reaction. The K-IE and Cu-IWI catalysts appeared to be the most promising ones, although further improvements in catalytic activity will be desirable. Some surprising results regarding CO and CO₂ selectivity are also reported, especially for Co catalysts.

In VOC combustion, the effect of the nature of ion B (Fe and Ni) on the partial substitution of ion A (Ca for La) in ABO₃ perovskites (e.g., LaFeO₃ and LaNiO₃) and on their catalytic activity was studied. The perovskite-type oxides were characterized by means of surface area measurements, XRD, temperature-programmed desorption (TPD) and temperature-programmed reduction (TPR). The effect of partial substitution of La³⁺ by Ca²⁺ was more significant for the La_1−xCa_xFeO₃ perovskites. In this case, the electronic perturbation is compensated by an oxidation state increase of part of Fe³⁺ to Fe⁴⁺. The TPD results revealed that, at higher substitution levels, oxygen vacancies are also formed to preserve electroneutrality. For the La_1−xCa_xNiO₃ perovskites, the characterization results showed no evidence of large differences in electronic properties as calcium substitution increases. The La_1−xCa_xNiO₃ perovskites exhibited lower activity than the simple LaNiO₃ perovskite, whereas for the La_1−xCa_xFeO₃ substituted perovskites the most active catalyst (exhibiting the lowest ignition temperature) was obtained at the highest substitution level, La_0.6Ca_0.4FeO₃.

The performance of both groups of catalysts is briefly discussed in terms of redox processes, in which the interplay between oxygen transfer and electron transfer requires further elucidation for the improvement of catalytic activity.     

Reactor and in situ FTIR studies of Pt/BaO/Al2O3 and Pd/BaO/Al2O3 NOx storage and reduction (NSR) catalysts

The reduction of NO under cyclic “lean”/“rich” conditions was examined over two model 1 wt.% Pt/20 wt.% BaO/Al₂O₃ and 1 wt.% Pd/20 wt.% BaO/Al₂O₃ NO_x storage reduction (NSR) catalysts. At temperatures between 250 and 350 °C, the Pd/BaO/Al₂O₃ catalyst exhibits higher overall NO_x reduction activity. Limited amounts of N₂O were formed over both catalysts. Identical cyclic studies conducted with non-BaO-containing 1 wt.% Pt/Al₂O₃ and Pd/Al₂O₃ catalysts demonstrate that under these conditions Pd exhibits a higher activity for the oxidation of both propylene and NO. Furthermore, in situ FTIR studies conducted under identical conditions suggest the formation of higher amounts of surface nitrite species on Pd/BaO/Al₂O₃. The IR results indicate that this species is substantially more active towards reaction with propylene. Moreover, its formation and reduction appear to represent the main pathway for the storage and reduction of NO under the conditions examined. Consequently, the higher activity of Pd can be attributed to its higher oxidation activity, leading both to a higher storage capacity (i.e., higher concentration of surface nitrites under “lean” conditions) and a higher reduction activity (i.e., higher concentration of partially oxidized active propylene species under “rich” conditions). The performance of Pt and Pd is nearly identical at temperatures above 375 °C.     

Oxygen storage capacity of La1−xBO3 perovskites (with A′ = Sr, Ce; B = Co, Mn)—relation with catalytic activity in the CH4 oxidation reaction

The aim of this work was to study the effect of cation-substitution on the reducibility of the perovskite, as well as the effect on the catalytic activity for the CH₄ oxidation reaction. Six perovskites (LaCoO₃, LaMnO₃, La_1−xSr_xMnO₃ (x = 0.2, 0.4), and La_1−xCe_xMnO₃ (x = 0.05, 0.1)) were synthesized by reactive grinding. The reducibility of the perovskite was studied by means of the oxygen storage capacity (OSC) measurement. OSC was performed at different temperatures on LaCoO₃ and LaMnO₃, in order to elucidate the different mechanisms of reduction involved at each temperature. The substituted samples showed that reduction profile is modified at high-substitution degrees; however, no differences were observed on the OSC values (amount of most active oxygen, calculated after one pulse of CO) between the pure lanthanum sample and the substituted ones.

Tested in the CH₄ oxidation reaction, the LaCoO₃ sample was found to present a little higher activity than LaMnO₃, even if the cobalt-based sample presented a smaller specific surface area. Moreover, all the substituted samples presented very slightly higher activities than the pure LaMnO₃ solid. Because of the supposed redox oxidation mechanism (Mars-Van-Krevelen), this agrees well with the OSC results obtained for the reducibility of the manganese on these samples, by which it was observed that substitution does not clearly affect the immediate reduction of the manganese.     

Ethanol combustion over strontium- and cerium-doped LaCoO3 catalysts

Ce- or Sr-doped LaCoO₃ bulk perovskites were prepared by citric acid method as well as 10 wt.% of LaCoO₃ was deposited on alumina carrier stabilized with lanthanum. Properties of prepared materials were characterized by determination of surface area, acid-basic properties and XRD, XPS, TPDO₂, H₂-TPR measurements as well as catalytic activity and selectivity for ethanol combustion was tested. It was found that substitution of La in LaCoO₃ with either Sr or Ce has only small effect on its activity in ethanol combustion. Strontium inserted into LaCoO₃ structure increases basic character of the perovskite surface as well as selectivity to acetaldehyde (ACA). Substitution of La with cerium has no effect on the concentration of basic sites and does not affect the selectivity to ACA. Activity of LaCoO₃-based catalysts in ethanol combustion and their selectivity to ACA formation can be explained on the basis of the presence of both -oxygen species and sites with basic character on the material surface.

Acid-basic properties of supported LaCoO₃ are dominated by acidic character of the carrier. Results of XPS and H₂-TPR measurements of LaCoO₃ supported on La–Al₂O₃ suggest that perovskite remains in strong interaction with carrier and probably is partially decomposed. Deposition of perovskite on stabilized carrier significantly increases the rate of ethanol combustion.     

Monodispersed gold nanoparticles supported on γ-Al2O3 for enhancement of low-temperature catalytic oxidation of CO

Monodispersed nano-Au/γ-Al₂O₃ catalysts for low-temperature oxidation of CO have been prepared via a modified colloidal deposition route, which involves the deposition of dodecanethiolate self-assembled monolayer (SAM)-protected gold nanoparticles (C₁₂ nano-Au) in hexane on γ-Al₂O₃ at room temperature. The diameter of the gold nanoparticles deposited on the support is 2.5 ± 0.8 nm after thermal treatment, and their valence states comprise both the metallic and oxidized states. It is found that the thermal treatment temperature affects significantly the catalytic activity of the catalysts in the processing steps. The catalyst treated at 190 °C exhibits considerably higher activity as compared to catalysts treated at 165 and 250 °C. A 2.0-wt.% nano-Au/γ-Al₂O₃ catalyst treated at 190 °C for 15 h maintains the catalytic activity at nearly 100% CO oxidation for at least 800 h at 15 °C, at least 600 h at 0 °C, and even longer than 450 h at −5 °C. Evidently, the catalysts obtained using this preparation route show high catalytic activity, particularly at low temperatures, and a good long-term stability.     

Gold supported on ceria and ceria–alumina promoted by molybdena for complete benzene oxidation

New gold–molybdena catalysts supported on ceria and ceria–alumina in reaction of complete benzene oxidation were studied. The catalysts were characterized by means of XRD, TPR, XPS and Raman spectroscopy. High and stable catalytic activity was established in the temperature region 200–240 °C. The presence of gold causes a modification in ceria structure leading to an increase of Ce³⁺ and oxygen vacancies formation. The loading of Al³⁺ increases additionally the oxygen vacancies, while a tendency of decrease of Ce³⁺ amount was observed. The presence of alumina results also in a larger share of active oxygen species proved by analysis of O 1s XPS spectra. The differences in the activities within the starting temperature range (150–180 °C) and in the region of 100% conversion (200–240 °C) could be explained by supposing that in the LT region the electron transfer between nanosized gold and ceria particles via oxygen vacancies has a crucial role. In the HT region the oxygen mobility, provoked by the defective structure of ceria due to the presence of Al³⁺, becomes of prevailing importance. It was also concluded that alumina prevents the gold and ceria agglomeration, which is the main factor to avoid deactivation under extreme reaction conditions.     

A comparative study of the water-gas shift activity of Pt catalysts supported on single (MOx) and composite (MOx/Al2O3, MOx/TiO2) metal oxide carriers

The water-gas shift (WGS) activity of platinum catalysts dispersed on a variety of single metal oxides as well as on composite MO_x/Al₂O₃ and MO_x/TiO₂ supports (M = Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, La, Ce, Nd, Sm, Eu, Gd, Ho, Er, Tm) has been investigated in the temperature range of 150–500 °C, using a feed composition consisting of 3% CO an 10% H₂O. For Pt catalysts supported on single metal oxides, it has been found that both the apparent activation energy of the reaction and the intrinsic rate depend strongly on the nature of the support. In particular, specific activity of Pt at 250 °C is 1–2 orders of magnitude higher when supported on “reducible” compared to “irreducible” metal oxides. For composite Pt/MO_x/Al₂O₃ and Pt/MO_x/TiO₂ catalysts, it is shown that the presence of MO_x results in a shift of the CO conversion curve toward lower reaction temperatures, compared to that obtained for Pt/Al₂O₃ or Pt/TiO₂, respectively. The specific reaction rate is in most cases higher for composite catalysts and varies in a manner which depends on the nature, loading, and primary crystallite size of dispersed MO_x. Results are explained by considering that reducibility of small oxide particles increases with decreasing crystallite size, thereby resulting in enhanced WGS activity. Therefore, evidence is provided that the metal oxide support is directly involved in the WGS reaction mechanism and determines to a significant extent the catalytic performance of supported noble metal catalysts. Results of catalytic performance tests obtained under realistic feed composition, consisting of 3% CO, 10% H₂O, 20% H₂ and 6% CO₂, showed that certain composite Pt/MO_x/Al₂O₃ and Pt/MO_x/TiO₂ catalysts are promising candidates for the development of active WGS catalysts suitable for fuel cell applications.     

Effect of Ru on LaCoO3 perovskite-derived catalyst properties tested in oxidative reforming of diesel

The oxidative reforming of diesel over Co/La₂O₃ and Ru–Co/La₂O₃ catalysts derived from LaCoO₃ perovskite precursors was studied. Physicochemical characterization by XPS, TPR and XRD revealed that the incorporation of Ru to LaCoO₃ produces changes in LaCoO₃ evidenced by a smaller size of the LaCoO₃ particles and cobalt segregation on the LaCoO₃ surface. The modifications in the structure of LaCoO₃ induced by the addition of Ru directly affect the dispersion and morphology of Co particles developed under the reaction. The active phases derived from pretreatment of perovskites evolve differently with time on stream, being observed that the presence of a greater proportion of perovskite phase in the Ru/LaCoO₃ sample produces an increase in catalyst stability. TPD-MS analysis also indicates that bulk oxygen release from the Ru–Co/La₂O₃ sample could improve its catalytic behaviour. The characterization of used samples reveals that improvements in the cobalt surface concentration and Co–La₂O₃ interactions contribute to the better catalytic stability of the Ru–Co/La₂O₃-derived catalyst.     

Supported base metal catalysts for the preferential oxidation of carbon monoxide in the presence of excess hydrogen (PROX)

Supported base metal catalysts were tested for the preferential oxidation of CO (CO PROX). The catalysts we investigated covered a wide range of transition metals (Co, Cr, Cu, Ni, Zn) supported on oxides with very different acidic, basic and redox properties (MgO, La₂O₃, SiO₂–Al₂O₃, CeO₂, Ce_0.63Zr_0.37O₂). The influence of the metal loading (Cu), the support properties (acidity, basicity, redox, surface area) and the reaction conditions (reaction temperature, feed composition) on the catalyst activity and selectivity was evaluated. The activity of ceria and ceria–zirconia supported copper catalysts was comparable to the performances of noble metal samples classically used for the PROX reaction. In addition, Cu–CeO₂ catalysts showed a practically constant and high selectivity towards CO oxidation in the temperature range of 50–150 °C. Due to the strong synergetic effect between copper and ceria, only a small amount of copper (0.3 wt.%) was necessary to get an active catalyst. The best catalytic performances were obtained for the samples containing 1–3 wt.% copper. The presence of small copper particles in close interaction with the ceria support was shown to be responsible for the enhanced activity. Except for the hydrogen oxidation, no parallel reactions (CO or CO₂ methanation reactions, coking, RWGS) could be detected over these catalysts. Classically, an increase of the oxygen excess led to an increased CO conversion with a simultaneous loss of selectivity towards CO₂. Finally, the presence of CO₂ in the feed negatively affected the catalytic activity. This effect was attributed to the adsorption of CO₂ on the copper sites, probably as CO.     

Catalytic combustion over platinum group catalysts: fuel-lean versus fuel-rich operation

Performance data are presented for methane oxidation on alumina-supported Pd, Pt, and Rh catalysts under both fuel-rich and fuel-lean conditions. Catalyst activity was measured in a micro-scale isothermal reactor at temperatures between 300 and 800 °C. Non-isothermal (near adiabatic) temperature and reaction data were obtained in a full-length (non-differential) sub-scale reactor operating at high pressure (0.9 MPa) and constant inlet temperature, simulating actual reactor operation in catalytic combustion applications.

Under fuel-lean conditions, Pd catalyst was the most active, although deactivation occurred above 650 °C, with reactivation upon cooling. Rh catalyst also deactivated above 750 °C, but did not reactivate. Pt catalyst was active above 600 °C. Fuel-lean reaction products were CO₂ and H₂O for all three catalysts.

The same catalysts tested under fuel-rich conditions demonstrated much higher activity. In addition, a ‘lightoff’ temperature was found (between 450 and 600 °C), where a stepwise increase in reaction rate was observed. Following ‘lightoff’ partial oxidation products (CO, H₂) appeared in the mixture, and their concentration increased with increasing temperature. All three catalysts exhibited this behavior.

High-pressure (0.9 MPa) sub-scale reactor and combustor data are shown, demonstrating the benefits of fuel-rich operation over the catalyst for ultra-low emissions combustion.     

AMnO3 (A=La, Nd, Sm) and Sm1−xSrxMnO3 perovskites as combustion catalysts: structural, redox and catalytic properties

Catalytic combustion of methane has been investigated over AMnO₃ (A = La, Nd, Sm) and Sm_1−xSr_xMnO₃ (x = 0.1, 0.3, 0.5) perovskites prepared by citrate method. The catalysts were characterized by chemical analysis, XRD and TPR techniques. Catalytic activity measurements were carried out with a fixed bed reactor at T = 623–1023 K, space velocity = 40 000 N cm³ g⁻¹ h⁻¹, CH₄ concentration = 0.4% v/v, O₂ concentration = 10% v/v.

Specific surface areas of perovskites were in the range 13–20 m² g⁻¹. XRD analysis showed that LaMnO₃, NdMnO₃, SmMnO₃ and Sm_1−xSr_xMnO₃ (x = 0.1) are single phase perovskite type oxides. Traces of Sm₂O₃ besides the perovskite phase were detected in the Sm_1−xSr_xMnO₃ catalysts for x = 0.3, 0.5. Chemical analysis gave evidence of the presence of a significant fraction of Mn(IV) in AMnO₃. The fraction of Mn(IV) in the Sm_1−xSr_xMnO₃ samples increased with x. TPR measurements on AMnO₃ showed that the perovskites were reduced in two steps at low and high temperature, related to Mn(IV) → Mn(III) and Mn(III) → Mn(II) reductions, respectively. The onset temperatures were in the order LaMnO₃ > NdMnO₃ > SmMnO₃. In Sm_1−xSr_xMnO₃ the Sr substitution for Sm caused the formation of Mn(IV) easily reducible to Mn(II) even at low temperature. Catalytic activity tests showed that all samples gave methane complete conversion with 100% selectivity to CO₂ below 1023 K. The activation energies of the AMnO₃ perovskites varied in the same order as the onset temperatures in TPR experiments suggesting that the catalytic activity is affected by the reducibility of manganese. Sr substitution for Sm in SmMnO₃ perovskites resulted in a reduction of activity with respect to the unsubstituted perovskite. This behaviour was related to the reduction of Mn(IV) to Mn(II), occurring under reaction conditions, hindering the redox mechanism.     

Combustion synthesis of perovskite-type catalysts for natural gas combustion

Combustion synthesis has been applied to LaMnO₃ production with a view to boosting its activity towards natural gas combustion by enhancing its specific surface area. With a highly exothermic and self-sustaining reaction, this oxide can be quickly prepared from an aqueous solution of metal nitrates (oxidisers) and urea (fuel).

The favourable conditions for LaMnO₃ formation were sought: only fuel-rich mixtures are effective, but carbonaceous deposits are formed when too much urea is used. In the field of operating conditions in which the combustion synthesis reaction takes place, the specific surface areas were not dramatically higher than those obtained with traditional methods; moreover, even short thermal treatments have been found to rapidly deactivate the catalysts by rapid sintering. With a view to tackling these problems, NH₄NO₃ was chosen as an additive for its low costs, highly exothermic decomposition and because it generates gaseous products only, without altering the proportion of the other elements in the catalysts. With ammonium nitrate, specific area was enhanced from 4 m²/g up to about 20 m²/g. A short thermal treatment at 900 °C partially deactivates also the NH₄NO₃-derived catalysts. It was found that NH₄NO₃-boosted mixtures produce materials whose activity, after a similar thermal treatment, behave practically as the perovskites obtained by the “citrates” method.

Combustion synthesis is though rather cheap—in terms of reactants employed—and quick, given that the process requires few minutes at low temperature without successive calcination. However, the main drawback of this method is that hazardous or polluting compounds are emitted during the synthesis (mainly NH₃ or NO_x).

The MgO introduction, which should act both as a structural promoter and as a sulphur poisoning limiting agent, has proved to be harmful: since MgO does not physically interpose between perovskite grains, it does not offer resistance to deactivation induced by high temperatures.     

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.     

Well-dispersed perovskite-type oxidation catalysts

A novel technique for the preparation of highly dispersed rare-earth perovskite LaCoO₃ catalysts was developed. Using the conventional complexation and pyrolysis methods, an etchable component, zinc oxide (ZnO), was introduced into the precursor by adding zinc nitrate during preparation. After calcination, the independent ZnO phase was extracted by an aqueous NH₄Cl solution, resulting in well-dispersed LaCoO₃ catalysts with a surface area of over 30 m²/g. DTA-reaction tests using CO oxidation as the model reaction were performed as a quick means to illustrate the higher catalytic oxidation activities of the prepared LaCoO₃ catalysts mainly due to their high surface area.