Synthesis and catalytic properties of Ce0.6Zr0.4O2 solid solutions in the oxidation of soluble organic fraction from diesel engines

Ce_0.6Zr_0.4O₂ solid solutions were synthesized by co-precipitation, sol–gel like method, solution combustion and surfactant-assistant approaches, respectively. The catalytic properties of bulk and γ-Al₂O₃ supported Ce_0.6Zr_0.4O₂ solid solutions were studied for the oxidation of soluble organic fractions (SOF) from diesel engines by TG-DTA method. The physicochemical properties were characterized by XRD, BET surface area and pore distribution, SEM, TEM, and particle size distribution techniques. XRD and TEM results show that a Ce_0.6Zr_0.4O₂ solid solution was formed for samples as-prepared and heat-treated at 900 °C for 2 h in air. The co-precipitation derived Ce_0.6Zr_0.4O₂ has as high BET surface area as 153.71 m²/g by controlling preparation conditions. Notable is that the surface area and particle size for fresh Ce_0.6Zr_0.4O₂ ignited at 350 °C decreased little after a thermal treatment in air at 900 °C for 2 h. Furthermore, its bulk density is lowest. The commercial engine oil (SJ5W/40) for FAW-VOLKSWAGEN, which was used by Bora 1.9 TDI diesel cars in China market was substituted for SOF. The catalytic activity was evaluated by normalized peak areas and extrapolated onset temperatures of DTA curves. A computer program was developed by direct non-linear regression model for simulation of TG/DTG curves to determine the thermal processes and kinetic parameters. It is found that lube evaporation/decomposition and thermal decomposition (pyrolysis) were observed under a nitrogen atmosphere. Lube evaporation fractions were inhibited by Ce_0.6Zr_0.4O₂ and γ-Al₂O₃. While under an air atmosphere, namely, in the process of lube oxidation (combustion), evaporation/decomposition, low-temperature oxidation and high-temperature oxidation were distinguished. Ce_0.6Zr_0.4O₂ solid solutions are active catalysts for lube oxidation, in which the sample prepared by solution combustion has the highest activity, mainly due to the maintenance of the surface area and particle size upon sintering and its lowest bulk density. However, γ-Al₂O₃ is more like a support. There exists synergism between Ce_0.6Zr_0.4O₂ and γ-Al₂O₃: γ-Al₂O₃ adsorbs lube retaining it within its pore structure, whereas, Ce_0.6Zr_0.4O₂ solid solutions initiate oxidation reactions when light-off temperatures reach. The application of CeO₂-ZrO₂ solid solution prepared by solution combustion at lower temperature would be promising in diesel oxidation catalysts.     

Preparation of CexZr1−xO2 (x = 0.75, 0.62) solid solution and its application in Pd-only three-way catalysts

Nanoparticles of Ce_xZr_1−xO₂ (x = 0.75, 0.62) were prepared by the oxidation-coprecipitation method using H₂O₂ as an oxidant, and characterized by N₂ adsorption, XRD and H₂-TPR. Ce_xZr_1−xO₂ prepared had single fluorite cubic structure, good thermal stability and reduction property. With the increasing of Ce/Zr ratio, the surface area of Ce_xZr_1−xO₂ increased, but thermal stability of Ce_xZr_1−xO₂ decreased. The surface area of Ce_0.62Zr_0.38O₂ was 41.2 m²/g after calcination in air at 900 °C for 6 h. TPR results showed the formation of solid solution promoted the reduction of CeO₂, and the reduction properties of Ce_xZr_1−xO₂ were enhanced by the cycle of TPR-reoxidation. The Pd-only three-way catalysts (TWC) were prepared by the impregnation method, in which Ce_0.75Zr_0.25O₂ was used as the active washcoat and Pd loading was 0.7 g/L. In the test of Air/Fuel, the conversion of C₃H₈ was close to 100% and NO was completely converted at λ < 1.025. The high conversion of C₃H₈ was induced by the steam reform and dissociation adsorption reaction of C₃H₈. Pd-only catalyst using Ce_0.75Zr_0.25O₂ as active washcoat showed high light off activity, the reaction temperatures (T₅₀) of 50% conversion of CO, C₃H₈ and NO were 180, 200 and 205 °C, respectively. However, the conversions of C₃H₈ and NO showed oscillation with continuously increasing the reaction temperature. The presence of La₂O₃ in washcoat decreased the light off activity and suppressed the oscillation of C₃H₈ and NO conversion. After being aged at 900 °C for 4 h, the operation windows of catalysts shifted slightly to rich burn. The presence of La₂O₃ in active washcoat can enhance the thermal stability of catalyst significantly.     

Methanol decomposition to synthesis gas at low temperature over palladium supported on ceria–zirconia solid solutions

The Ce_xZr_1−xO₂ solid solution was used as a support of a palladium catalyst for methanol decomposition to synthesis gas at low temperature. All Pd-containing catalysts tested in this study showed high selectivity to synthesis gas (over 96%). The Pd supported on the composite oxide with a Ce/Zr molar ratio of 4/1 exhibited the highest activity. Pd/Ce_0.8Zr_0.2O₂ (17 wt.%) (cop) (prepared by coprecipitation method) showed a conversion of 51.2% for the methanol decomposition at 473 K, which was higher than those over 17 wt.% Pd/CeO₂ (cop) (40.7%) and 17 wt.% Pd/ZrO₂ (cop) (24.3%) at 473 K. The 17 wt.% Pd/Ce_0.8Zr_0.2O₂ (cop) catalyst showed a higher BET surface area and smaller Pd particles than those of 17 wt.% Pd/CeO₂ (cop). Moreover, a more active Pd^σ+ state could be maintained by Zr⁴⁺ ion modification due to promotion of the oxygen mobility and enhancement of the reductibility and increase in the acid sites of the CeO₂ support. The 17 wt.% Pd/Ce_0.8Zr_0.2O₂ (cop) catalyst showed a much higher conversion (51.2%) than that over 17 wt.% Pd/Ce_0.8Zr_0.2O₂ (imp) (prepared by impregnation method) (17.2%) at 473 K. This is due to the 17 wt.% Pd/Ce_0.8Zr_0.2O₂ (cop) possessing many small Pd particles. The 17 wt.% Pd/Ce_0.8Zr_0.2O₂ (cop) catalyst showed an initial conversion of 51.2% at 473 K but the conversion decreased to 43.1% after 24 h on stream. This deactivation was attributed to carbonaceous deposit on the catalyst surface. The amounts of coke on the 17 wt.% Pd/Ce_0.8Zr_0.2O₂ (cop) catalyst were 0.9 wt.% after 24 h on stream at 473 K and 2.1 wt.% after 1 h on stream at 523 K.     

Investigation of the oxygen storage process on ceria- and ceria–zirconia-supported catalysts

A total of 10 noble metal (Rh, Pt, Pd, Ru and Ir) catalysts, either supported on CeO₂ or Ce_0.63Zr_0.37O₂, were prepared. Catalysts were fully characterized using XRD, N₂ adsorption at −196 °C, TEM and H₂ chemisorption. Oxygen storage processes were carefully investigated. The influence of temperature was checked and a key role of oxygen diffusion was further demonstrated. A review of the reactions involved in the CO transient oxidation reaction is finally proposed.     

Partial oxidation and combined reforming of methane on Ce-promoted catalysts

Pt/ZrO₂ and Pt/Ce_0.14Zr_0.86O₂ catalysts containing 0.5 and 1.5 wt.% Pt were studied in order to evaluate the effect of the support reducibility and metal dispersion on the catalyst stability for the partial oxidation and the combined partial oxidation and CO₂ reforming of methane. The Pt/Ce_0.14Zr_0.86O₂ catalysts proved to be more active, stable and selective than Pt/ZrO₂ catalysts during the partial oxidation reaction. No increase in deactivation was observed when the CH₄:O₂ feed ratio was increased from 2:1 to 4:1. In addition, no water formation was observed at the high CH₄:O₂ ratios. The activity of the catalyst is dependent upon both the dispersion and the ability of the catalyst to resist carbon deposition.

The addition of CO₂ resulted in a decrease in the methane conversion and a decrease in the H₂/CO ratio for the Ce_0.14Zr_0.86O₂ and ZrO₂ supported catalysts. Small increases in the temperature of the bed have been recorded during the partial oxidation reaction. However, within a few minutes the temperature stabilizes below the furnace temperature providing indirect evidence for the combined combustion and reforming mechanisms previously proposed. The 1.5 wt.% Pt/CeZrO₂ catalyst shows promise for the autothermal reforming reaction based on the stability during transient operation.     

Catalytic reduction of sulfur dioxide using hydrogen or carbon monoxide over Ce1−xZrxO2 catalysts for the recovery of elemental sulfur

This study focuses on the direct sulfur recovery process (DSRP), in which SO₂ can be directly converted into elemental sulfur using a variety of reducing agents over Ce_1−xZr_xO₂ catalysts. Ce_1−xZr_xO₂ catalysts (where x = 0.2, 0.5, and 0.8) were prepared by a citric complexation method. The experimental conditions used for SO₂ reduction were as follow: the space velocity (GHSV) was 30,000 ml/g_-cat h and the ratio of [CO (or H₂, H₂ + CO)]/[SO₂] was 2.0. It was found that the catalyst and reducing agent providing the best performance were the Ce_0.5Zr_0.5O₂ catalyst and CO, respectively. In this case, the SO₂ conversion was about 92% and the sulfur yield was about 90% at 550 °C. Also, a higher efficiency of SO₂ removal and elemental sulfur recovery was achieved in the reduction of SO₂ with CO as a reducing agent than that with H₂. In the reduction of SO₂ by H₂ over the Ce_0.5Zr_0.5O₂ catalyst, SO₂ conversion and sulfur yield were about 92.7% and 73%, respectively, at 800 °C. Also, the reduction of SO₂ using synthetic gas with various [CO]/[H₂] molar ratios over the Ce_0.5Zr_0.5O₂ catalyst was performed, in order to investigate the possibility of using coal-derived gas as a reducing agent in the DSRP. It was found that the reactivity of the SO₂ reduction using the synthetic gas with various [CO]/[H₂] molar ratios was increased with increasing CO content of the synthetic gas. Therefore, it was found that the Ce_1−xZr_xO₂ catalysts are applicable to the DSRP using coal-derived gas, which contains a larger percentage of CO than H₂.     

Catalytic purification of waste gases containing VOC mixtures with Ce/Zr solid solutions

This study has been undertaken to investigate the efficiency of ceria, zirconia, and Ce_xZr_1−xO₂ mixed oxides as catalysts for the vapour-phase destruction in air of single model VOCs (n-hexane, 1,2-dichloroethane and trichloroethylene) and non-chlorinated VOC/chlorinated VOC binary mixtures. Considering all catalyst compositions examined for the individual destruction of these compounds, activity for complete oxidation decreased in the following order: n-hexane < 1,2-dichloroethane < trichloroethylene. The compositions with the best performance for chlorinated VOCs abatement (Ce_0.5Zr_0.5O₂ and Ce_0.15Zr_0.85O₂) were different than that with the best performance for n-hexane oxidation (CeO₂). Concerning chlorinated VOCs conversion, it was observed that notable improvements in catalyst activity of CeO₂ could be achieved through structural doping with Zr ions. Mixed oxides exhibited promoted redox and acid properties, which resulted catalytically relevant for the oxidation of 1,2-dichloroethane and trichloroethylene. In contrast, the combustion of n-hexane was essentially controlled by surface oxygen species, which were more abundant on CeO₂. Attainment of high n-hexane conversions with CeO₂ was also attributed in part to the hydrophobicity of the support and the reduced interaction with carbon dioxide.

Significant ‘mixture effects’ on both activity and selectivity were noticed when a given chlorinated feed was decomposed in the presence of n-hexane. On one hand, each VOC decreased the reactivity of the other relative to that of the pure compound resulting in higher operating temperatures to achieve adequate destruction. Competitive adsorption played an important role in the reciprocal inhibition effects detected with all catalysts. On the other hand, the selectivity to HCl was noticeably enhanced when n-hexane was co-fed, probably due to the increased presence of water generated as an oxidation product.     

Pd/Ce0.6Zr0.4O2/Al2O3 as advanced materials for three-way catalysts: Part 1. Catalyst characterisation, thermal stability and catalytic activity in the reduction of NO by CO

Pd-loaded Ce_0.6Zr_0.4O₂ solid solutions supported on Al₂O₃ are investigated as catalysts for the reduction of NO by CO. The attention is focused on the role of the Ce_0.6Zr_0.4O₂ and of the Pd dispersion on the catalytic activity. The system shows a very high activity below 500 K, which is almost independent on the Pd dispersion. The high activity is attributed to a promoting effect of the Ce_0.6Zr_0.4O₂ on the NO conversion. Investigation of the influence of high temperature treatments disclosed a thermal stabilisation of both Ce_0.6Zr_0.4O₂ and Al₂O₃ in the Ce_0.6Zr_0.4O₂/Al₂O₃ system.     

Ce1−xCuxO2−x/Al2O3/FeCrAl catalysts for catalytic combustion of methane

A series of the Ce_1−xCu_xO_2−x/Al₂O₃/FeCrAl catalysts (x = 0–1) were prepared. The structure of the catalysts was characterized using XRD, SEM and H₂-TPR. The catalytic activity of the catalysts for the combustion of methane was evaluated. The results indicated that in the Ce_1−xCu_xO_2−x/Al₂O₃/FeCrAl catalysts the surface phase structure were the Ce_1−xCu_xO_2−x solid solution, -Al₂O₃ and γ-Al₂O₃. The surface particle shape and size were different with the variety of the molar ratio of Ce to Cu in the Ce_1−xCu_xO_2−x solid solution. The Cu component of the Ce_1−xCu_xO_2−x/Al₂O₃/FeCrAl catalysts played an important role to the catalytic activity for the methane combustion. There were the stronger interaction among the Ce_1−xCu_xO_2−x solid solution and the Al₂O₃ washcoats and the FeCrAl support.     

Performance and characterization of supported metal catalysts for complete oxidation of formaldehyde at low temperatures

Activities of a series of metals (Pt, Pd, Rh, Cu, Mn) supported on TiO₂ were investigated for the catalytic oxidation of formaldehyde. Among them, Pt/TiO₂ was found to be the most promising catalyst. Nitrogen adsorption, hydrogen chemisorption, X-ray diffraction (XRD), transmission electron microscopy (TEM) and temperature programmed reduction (TPR) by H₂ were used to characterize the platinum catalysts. Using Ce_0.8Zr_0.2O₂, Ce_0.2Zr_0.8O₂, SiO₂ as supports instead of TiO₂, the activity sequence of 0.6 wt.% platinum with respect to the supports is TiO₂ > SiO₂ > Ce_0.8Zr_0.2O₂ > Ce_0.2Zr_0.8O₂, and this appears to be correlated with the dispersion of platinum on supports rather than the specific surface areas of the catalysts. Platinum loading on TiO₂ has a great effect on the catalytic activity, and 0.6 wt.% Pt/TiO₂ catalyst was observed to be the most active, which could be attributed to the well-dispersed platinum surface phase. The reduction temperature greatly affects the particle size and, consequently, the catalytic activity. The smaller particle size of platinum, due to its high dispersion on support, has a positive effect on catalytic performance. Increasing formaldehyde concentration and space velocity exhibits an inhibiting effect on the catalytic activity.     

Defective structure, oxygen mobility, oxygen storage capacity, and redox properties of RE-based (RE = Ce, Pr) solid solutions

Defective structures, surface textures, oxygen mobility, oxygen storage capacity (OSC), and redox properties of RE_0.6Zr_0.4O₂ and of RE_0.6Zr_0.4−xY_xO₂ (RE=Ce, Pr; x=0, 0.05) solid solutions have been investigated using X-ray diffraction (XRD), temperature-programmed desorption (TPD), temperature-programmed reduction (TPR), O₂−H₂ and O₂−CO titration, ¹⁸O/¹⁶O isotope exchange, CO pulsing reaction, and X-ray photoelectron spectroscopy (XPS) techniques. The effects of doping noble metal onto RE_0.6Zr_0.4−xY_xO₂ on oxygen mobility and surface oxygen activities have also been studied. Based on the experimental outcomes, we conclude that: (i) a Pr-based solid solution has better redox behavior than a Ce-based one; (ii) incorporation of yttrium ions in the lattices of CZ and PZ solid solutions could result in an enhancement in oxygen vacancy concentration, Ce⁴⁺/Ce³⁺ and Pr⁴⁺/Pr³⁺ redox properties, lattice oxygen mobility, and oxygen storage capacity; and (iii) doping the noble metal (Rh, Pt, and Pd) onto RE-based solid solution has positive effect on the properties concerned in this work.     

Partial oxidation of ethane to synthesis gas over Co-loaded catalysts

Attention has been increasingly paid to the partial oxidation of lower alkanes to synthesis gas, due to its intrinsic energy saving process. We studied the partial oxidation of ethane (POE) on Co loaded on various supports. The POE performance varied as follows: Y₂O₃, CeO₂, ZrO₂, La₂O₃  SiO₂, Al₂O₃, TiO₂ > MgO. Comparing Y₂O₃ and CeO₂, the carbon deposition during the POE was negligible on CeO₂ and therefore CeO₂ was the most preferable support. By changing space velocity and O₂ partial pressure, reaction mechanism of POE was studied and it was revealed that two-step mechanism was prevailing; combustion of ethane to H₂O and CO₂ and subsequent reforming of ethane with H₂O and CO₂ to synthesis gas. Co/CeO₂ catalyst exhibited high and stable catalytic activity for 10 h; high ethane conversion of 18% (maximum ethane conversion 20% at O₂/C₂H₆ = 0.2) with H₂ and CO selectivities of 93 and 84%, respectively.     

铈锆固溶体CexZr1-xO2上H2S的选择性催化氧化性能

采用共沉淀法合成一系列具有不同Ce/Zr物质的量比的铈锆固溶体Ce_xZr_1-xO₂,考察Ce/Zr比例对H₂S选择氧化反应催化活性的影响。通过XRD、BET、Raman、XPS、CO₂-TPD、O₂-TPD、H₂-TPR等手段对铈锆固溶体的晶体结构、表面性质、碱性位以及氧化还原性等进行表征。结果表明,所有的铈锆固溶体催化剂均可以在化学计量比的氧气下具有优良的低温催化活性,催化活性随着Ce/Zr比例的提高而增加,其中Ce_0.9Zr_0.1O₂活性最高,(160~260) ℃转化率均保持在95%以上,在180 ℃时硫收率可达到97%,这主要是因为Ce_0.9Zr_0.1O₂具有最多的中度碱性位、活性位数量和强的氧化还原性。同时推测Ce⁴⁺为催化反应的活性位,并遵循氧化还原机理。此外,催化剂的失活主要是由于催化剂表面生成硫酸盐物种,消耗了活性组分Ce⁴⁺。     

Synthesis of CeO2–MnOx mixed oxides and catalytic performance under oxygen-rich condition

Ce_0.5Zr_0.5O₂, Ce_0.5Zr_0.2Mn_0.3O₂ and Ce_0.5Mn_0.5O₂ were prepared by citric acid sol–gel method. The effect of manganese on the structural and redox properties of ceria-based mixed oxides was investigated by means of powder X-ray diffraction, X-ray photoelectron spectroscopy, Brunauer–Emmett–Teller analyses, temperature-programmed reduction and catalytic activity evaluation in the presence of excess O₂. The results showed that some Mn cations could enter into the ceria lattice to form solid solutions. Mn₃O₄ appeared due to the instability of the mixed oxides with increment of the Mn doping ratio while another oxide Mn₂O₃ is detected in the physical mixture of ceria and manganese oxide. These Mn-doped mixed oxides, especially Ce_0.5Mn_0.5O₂, presented better catalytic activities than Ce_0.5Zr_0.5O₂ and even Pt-loaded catalyst for total oxidation of C₃H₈ and oxidative sorption of NO in the presence of excess oxygen. The oxidation ability of Mn and the strong interaction between Mn and Ce were suggested to promote the oxygen storage/transport capacity of the mixed oxides as well as reactive adsorption of nitric oxide and hydrocarbons.     

Catalytic oxidation of VOCs on Au/Ce-Ti-O

Ce_xTi_1−xO₂ oxides have been synthesised by sol–gel method with x varying from 0 to 0.3 and characterised by XRD and TPR. The structure of oxides changes with the Ce/Ti molar ratio. The presence of ceria in Ce-Ti oxides inhibits the phase transition from anatase to rutile. When x = 0.3 (Ce_0.3Ti_0.7O₂ sample), the solid presents an amorphous state. The TPR results indicate that the presence of Ti enhances the reducibility of cerium oxide species. Catalytic oxidation of propene is investigated on Ce-Ti oxides and the better conversion is obtained with Ce_0.3Ti_0.7O₂ but the CO₂ selectivity reaches 63% at 400 °C. Gold is then deposited on theses oxides to improve the catalytic activity. On the basis of characterisation data (H₂ TPR), it has been suggested that gold influences the reduction of the Ce-Ti oxide support and the catalytic activity to the propene oxidation. Thus, Au/Ce-Ti-O system catalysts are promising catalysts for propene oxidation.     

Structure evolution of nanocrystalline CeO2 and CeLnOx mixed oxides (Ln = Pr, Tb, Lu) in O2 and H2 atmosphere and their catalytic activity in soot combustion

This paper reports results of studies on structure and activity in soot combustion of nanocrystalline CeO₂ and CeLnOx mixed oxides (Ln = Pr, Tb, Lu, Ce/Ln atomic ratios 5/1). Nano-sized (4–5 nm) oxides with narrow size distribution were prepared by a microemulsion method W/O. Microstructure, morphology and reductivity of the oxides annealed up to 950 °C in O₂ and H₂ were analyzed by HRTEM, XRD, FT-IR, Raman spectroscopy and H₂-TPR. Obtained mixed oxides had fluorite structure of CeO₂ and all exhibited improved resistance against crystal growth in O₂, but only CeLuOx behaved better than CeO₂ in hydrogen.

The catalytic activity of CeO₂, CeLnOx and physical mixtures of CeO₂ + Ln₂O₃ in a model soot oxidation by air was studied in “tight contact” mode by using thermogravimetry. Half oxidation temperature T_1/2 for soot oxidation catalysed by nano-sized CeO₂ and CeLnOx was similar and ca. 100 °C lower than non-catalysed oxidation. However, the mixed oxides were much more active during successive catalytic cycles, due to better resistance to sintering. Physical mixtures of nanooxides (CeO₂ + Ln₂O₃) showed exceptionally high initial activity in soot oxidation (decrease in T_1/2 by ca. 200 °C) but degraded strongly in successive oxidation cycles. The high initial activity was due to the synergetic effect of nitrate groups present in highly disordered surface of nanocrystalline Ln₂O₃ and enhanced reductivity of nanocrystalline CeO₂.     

The oxidizing role of CO2 at mild temperature on ceria-based catalysts

For thermodynamic reasons, CO₂ has always been considered as inert at mild reaction temperatures (300 °C). In this study, we show that CO₂ may be used as a valuable compound for the catalytic combustion of methane (CCM), if ceria-based materials are used as support for the palladium active phase. Adding CO₂ in the feed significantly improves performances of ceria-zirconia supported catalysts. On the contrary, catalytic performances are inhibited on Pd/γ-Al₂O₃. Inhibition can be avoided by mixing the Pd/γ-Al₂O₃ catalyst with some CeO₂ evidencing cooperation phenomena between both catalysts. In situ DRIFTS experiments show that the inhibition of the alumina-supported catalyst is not due to formation of carbonates species. After an in situ reducing pre-treatment, pure CO₂ is able to rapidly oxidize reduced Pd/Ce_0.21Zr_0.79O₂ catalyst at 300 °C. Dissociation of CO₂ on Ce_0.21Zr_0.79O₂ would be responsible for the oxidation process. Thus, CO₂ helps in replenishing the O reservoir (OSC) of the Ce-Zr-O support which is normally consumed by reductants such as CH₄, H₂ or other HC's. XPS experiments show enrichment in oxygen species bound to Ce (Low BE O1s) on the surface of ceria-zirconia when working in the presence of CO₂. Implications of these results on the behavior of ceria-containing catalysts can be important for practical applications, e.g., in automotive exhaust catalysis.     

Methane combustion and CO oxidation on LaAl1−xMnxO3 perovskite-type oxide solid solutions

Structural, redox and catalytic deep oxidation properties of LaAl_1−xMn_xO₃ (x=0.0, 0.05, 0.1, 0.2, 0.4, 0.6, 0.8, 1.0) solid solutions prepared by the citrate method and calcined at 1073 K were investigated. XRD analysis showed that all the LaAl_1−xMn_xO₃ samples are single phase perovskite-type solid solutions. Particle sizes and surface areas (SA) are in the 280–1180 Å and 4–33 m² g⁻¹ ranges, respectively. Redox properties and the content of Mn⁴⁺ were derived from temperature programmed reduction (TPR) with H₂. Two reduction steps are observed by TPR for pure LaMnO₃, the first attributed to the reduction of Mn⁴⁺ to Mn³⁺ and the second due to complete reduction of Mn³⁺ to Mn²⁺. The presence of Al in the LaAl_1−xMn_xO₃ solid solutions produces a strong promoting effect on the Mn⁴⁺→Mn³⁺ reducibility and inhibits the further reduction to Mn²⁺. Both for methane combustion and CO oxidation all Mn-containing perovskites are much more active than LaAlO₃, so pointing to the essential role of the transition metal ion in developing highly active catalysts. Partial dilution with Al appears to enhance the specific activity of Mn sites for methane combustion.     

Regeneration of thermally aged Pt-Rh/CexZr1−xO2-Al2O3 model three-way catalysts by oxychlorination treatments

Pt-Rh/Ce_xZr_1−xO₂-Al₂O₃ with 0.6 and 1.0 wt.% noble metal loadings were prepared and characterized for their metal dispersion with respect to Ce_xZr_1−xO₂-free Pt-Rh/Al₂O₃ in fresh, thermally aged and oxychlorinated states. Thermal ageing at 973 K led to loss of metal dispersion in all cases but to negligible effect on the dispersion of the Ce_xZr_1−xO₂ component where present. Oxychlorination was able to fully recover metal dispersion in all cases but led to different effects on the redox properties of Ce_xZr_1−xO₂ which appeared to be related to the metal loadings. Despite showing improved dispersion following regeneration, higher loaded catalyst showed no improvement in light-off performance for either NO reduction or CO oxidation and showed poorer oxygen storage (OSC) ability, particularly at higher temperatures. Lower loaded catalyst showed improved dispersion, improved OSC and reduced light-off temperatures for NO reduction and CO oxidation after oxychlorination compared to that in the thermally aged state.     

Syngas production from butane using a flame-made Rh/Ce0.5Zr0.5O2 catalyst

The capability of flame-made Rh/Ce_0.5Zr_0.5O₂ nanoparticles catalyzing the production of H₂- and CO-rich syngas from butane was investigated for different Rh loadings (0–2.0 wt% Rh) and two different ceramic fibers (Al₂O₃/SiO₂ and SiO₂) as plugging material in a packed bed reactor for a temperature range from 225 to 750 °C. The main goal of this study was the efficient processing of butane at temperatures between 500 and 600 °C for a micro-intermediate-temperature SOFC system. Our results showed that Rh/Ce_0.5Zr_0.5O₂ nanoparticles offer a very promising material for butane-to-syngas conversion with complete butane conversion and a hydrogen yield of 77% at 600 °C. The catalytic performance of packed beds strongly depended on the use of either Al₂O₃/SiO₂ or SiO₂ fiber plugs. This astonishing effect could be attributed to the interplay of homogeneous and heterogeneous chemical reactions during the high-temperatures within the reactor.