Role of CeO2 in Ni/CeO2–Al2O3 catalysts for carbon dioxide reforming of methane

Ni catalysts supported on γ-Al₂O₃, CeO₂ and CeO₂–Al₂O₃ systems were tested for catalytic CO₂ reforming of methane into synthesis gas. Ni/CeO₂–Al₂O₃ catalysts showed much better catalytic performance than either CeO₂- or γ-Al₂O₃-supported Ni catalysts. CeO₂ as a support for Ni catalysts produced a strong metal–support interaction (SMSI), which reduced the catalytic activity and carbon deposition. However, CeO₂ had positive effect on catalytic activity, stability, and carbon suppression when used as a promoter in Ni/γ-Al₂O₃ catalysts for this reaction. A weight loading of 1–5 wt% CeO₂ was found to be the optimum. Ni catalysts with CeO₂ promoters reduced the chemical interaction between nickel and support, resulting in an increase in reducibility and stronger dispersion of nickel. The stability and less coking on CeO₂-promoted catalysts are attributed to the oxidative properties of CeO₂.     

The effect of CeO2 structure on the activity of supported Pd catalysts used for methane steam reforming

Palladium (Pd) supported on CeO₂-promoted γ-Al₂O₃ with various CeO₂ (ceria) crystallinities, were used as catalysts in the methane steam reforming reaction. X-ray diffraction (XRD) analysis, FTIR spectroscopy of adsorbed CO, and X-ray photoelectron spectroscopy (XPS) were employed to characterize the samples in terms of Pd and CeO₂ structure and dispersion on the γ-Al₂O₃ support. These results were correlated with the observed catalytic activity and deactivation process. Arrhenius plots at steady-state conditions are presented as a function of CeO₂ structure. Pd is present on the oxidized CeO₂-promoted catalysts as Pd⁰, Pd⁺ and Pd²⁺, at ratios strongly dependent on CeO₂ structure. XRD measurements indicated that Pd is well dispersed (particles <2 nm) on crystalline CeO₂ and is agglomerated as large clusters (particles in 10–20 nm range) on amorphous CeO₂. FTIR spectra of adsorbed CO revealed that after pre-treatment under H₂ or in the presence of amorphous CeO₂, partial encapsulation of Pd particles occurs. CeO₂ structure influences the CH₄ steam reforming reaction rates. Crystalline CeO₂ and dispersed Pd favor high reaction rates (low activation energy). The presence of CeO₂ as a promoter conferred high catalytic activity to the alumina-supported Pd catalysts. The catalytic activity is significantly lower on Pd/γ-Al₂O₃ or on amorphous (reduced) CeO₂/Al₂O₃ catalysts. The reaction rates are two orders of magnitude higher on Pd/CeO₂/γ-Al₂O₃ than on Pd/γ-Al₂O₃, which is attributed to a catalytic synergism between Pd and CeO₂. The low rates on the reduced Pd/CeO₂/Al₂O₃ catalysts can be correlated with the loss of Pd sites through encapsulation or particle agglomeration, a process found mostly irreversible after catalyst regeneration.     

Low-temperature H2-SCR of NO on a novel Pt/MgO-CeO2 catalyst

The selective catalytic reduction of NO by H₂ under strongly oxidizing conditions (H₂-SCR) in the low-temperature range of 100–200 °C has been studied over Pt supported on a series of metal oxides (e.g., La₂O₃, MgO, Y₂O₃, CaO, CeO₂, TiO₂, SiO₂ and MgO-CeO₂). The Pt/MgO and Pt/CeO₂ solids showed the best catalytic behavior with respect to N₂ yield and the widest temperature window of operation compared with the other single metal oxide-supported Pt solids. An optimum 50 wt% MgO-50wt% CeO₂ support composition and 0.3 wt% Pt loading (in the 0.1–2.0 wt% range) were found in terms of specific reaction rate of N₂ production (mols N₂/g_cat s). High NO conversions (70–95%) and N₂ selectivities (80–85%) were also obtained in the 100–200 °C range at a GHSV of 80,000 h⁻¹ with the lowest 0.1 wt% Pt loading and using a feed stream of 0.25 vol% NO, 1 vol% H₂, 5 vol% O₂ and He as balance gas. Addition of 5 vol% H₂O in the latter feed stream had a positive influence on the catalytic performance and practically no effect on the stability of the 0.1 wt% Pt/MgO-CeO₂ during 24 h on reaction stream. Moreover, the latter catalytic system exhibited a high stability in the presence of 25–40 ppm SO₂ in the feed stream following a given support pretreatment. N₂ selectivity values in the 80–85% range were obtained over the 0.1 wt% Pt/MgO-CeO₂ catalyst in the 100–200 °C range in the presence of water and SO₂ in the feed stream. The above-mentioned results led to the obtainment of patents for the commercial exploitation of Pt/MgO-CeO₂ catalyst towards a new NO_x control technology in the low-temperature range of 100–200 °C using H₂ as reducing agent. Temperature-programmed desorption (TPD) of NO, and transient titration of the adsorbed surface intermediate NO_x species with H₂ experiments, following reaction, have revealed important information towards the understanding of basic mechanistic issues of the present catalytic system (e.g., surface coverage, number and location of active NO_x intermediate species, NO_x spillover).     

Surface properties and reactivity of Cu/γ-Al2O3 catalysts for NO reduction by C3H6: Influences of calcination temperatures and additives

The influences of calcination temperatures and additives for 10 wt.% Cu/γ-Al₂O₃ catalysts on the surface properties and reactivity for NO reduction by C₃H₆ in the presence of excess oxygen were investigated. The results of XRD and XPS show that the 10 wt.% Cu/γ-Al₂O₃ catalysts calcined below 973 K possess highly dispersed surface and bulk CuO phases. The 10 wt.% Cu/γ-Al₂O₃ and 10 wt.% Mn–10 wt.% Cu/γ-Al₂O₃ catalysts calcined at 1073 K possess a CuAl₂O₄ phase with a spinel-type structure. In addition, the 10 wt.% La–10 wt.% Cu/γ-Al₂O₃ catalyst calcined at 1073 K possesses a bulk CuO phase. The result of NO reduction by C₃H₆ shows that the CuAl₂O₄ is a more active phase than the highly dispersed and bulk CuO phase. However, the 10 wt.% Mn–10 wt.% Cu/γ-Al₂O₃ catalyst calcined at 1073 K possesses significantly lower reactivity for NO reduction than the 10 wt.% Cu/γ-Al₂O₃ catalyst calcined at 1073 K, although these catalysts possess the same CuAl₂O₄ phase. The low reactivity for NO reduction for 10 wt.% Mn–10 wt.% Cu/γ-Al₂O₃ catalyst calcined at 1073 K is attributed to the formation of less active CuAl₂O₄ phase with high aggregation and preferential promotion of C₃H₆ combustion to CO_x by MnO₂. The engine dynamometer test for NO reduction shows that the C₃H₆ is a more effective reducing agent for NO reduction than the C₂H₅OH. The maximum reactivity for NO reduction by C₃H₆ is reached when the NO/C₃H₆ ratio is one.     

Cu-Ce-O/γ-Al_2O_3的CO氧化性能

采用柠檬酸络合法制备一系列不同铜铈比的Cu-Ce-O/γ-Al_2O_3催化剂,用XRD、H2-TPR对其进行表征,采用连续固定床微反装置对Cu-Ce-O/γ-Al_2O_3催化剂CO催化氧化活性进行评价。结果表明,Cu-Ce-O/γ-Al_2O_3催化剂的XRD图谱中除归属于γ-Al_2O_3的晶相峰外,还出现CuO和CeO_2的晶相峰。高温水热引起活性组分CeO_2的晶粒聚集、长大和尖晶石结构CuAl2O4物质的生成;CuO-CeO_2之间的共生共存与相互作用,使得Cu-Ce-O/γ-Al_2O_3催化剂中具有非完整结构的[Cu2+1-xCu+x][O1-12x12x]增多,Cu+离子和氧空位增多,有利于其H2-TPR还原峰温度向低温区偏移,有利于提高其CO的催化氧化活性,使得Cu-Ce-O/γ-Al_2O_3催化剂的TCO50和TCO90降低。Cu与Ce物质的量比为5∶5制备的Cu-Ce-O/γ-Al_2O_3-55催化剂的TCO50和TCO90分别降至最低的162℃和199℃,表明此时的Cu-Ce-O协同效应最佳;CuO-CeO_2二相的共生共存与相互作用有利于减少高温水热环境下活性组分的聚集和晶粒长大,有利于Cu-Ce-O/γ-Al_2O_3催化剂能够保持较高的CO催化氧化活性。     

Interactions NO—CO and O2—NO—CO on CuCo2O4/γ-Al2O3 and on γ-Al2O3- and CuCo2O4/γ-Al2O3-supported Pt, Rh and Pt—Rh catalysts, a transient response study

The interactions NO—CO and O₂—NO—CO have been studied onCuCo₂O₄γ-Al₂O₃ and on γ-Al₂O₃- and CuCo₂O₄γ-Al₂O₃-supported Pt, Rh and Pt—Rh catalysts. The deposition of noble metals (Pt, Rh and Pt—Rh) on CuCo₂O₄γ-Al₂O₃ instead of γ-Al₂O₃ is beneficial in: lowering the temperature at which maximum N₂O is formed and decreasing the maximum N₂O concentration attained; lowering the onset temperature of NO to N₂ reduction, and increasing the N₂ selectivity; preserving the activity towards NO to N₂ reduction on a higher level following the concentration step NO + COO₂+ NO + CO and changing the conditions from stoichiometric to oxidizing (50% excess of oxidants). The reason for this behaviour of the CuCo₂O₄γ-Al₂O₃-based noble metal catalysts is the formation (reversible) of a reduced surface layer on the CuCo₂O₄ supported spinel under the conditions of a stoichiometric NO + CO mixture.     

Catalytic reduction of SO2 over supported transition-metal oxide catalysts with C2H4 as a reducing agent

This work investigates performances of supported transition-metal oxide catalysts for the catalytic reduction of SO₂ with C₂H₄ as a reducing agent. Experimental results indicate that the active species, the support, the feed ratio of C₂H₄/SO₂, and pretreatment are all important factors affecting catalyst activity. Fe₂O₃/γ-Al₂O₃ was found to be the most active catalyst among six γ-Al₂O₃-supported metal oxide catalysts tested. With Fe₂O₃ as the active species, of the supports tested, CeO₂ is the most suitable one. Using this Fe₂O₃/CeO₂ catalyst, we found that the optimal Fe content is 10 wt.%, the optimal feed ratio of C₂H₄/SO₂ is 1:1, and the catalyst presulfidized by H₂+H₂S exhibits a higher performance than those pretreated with H₂ or He. Although the feed concentrations of C₂H₄:SO₂ being 3000:3000 ppm provide a higher conversion of SO₂, the sulfur yield decreases drastically at temperatures above 300 °C. With higher feed concentrations, maximum yield appears at higher temperatures. The C₂H₄ temperature-programmed desorption (C₂H₄-TPD) and SO₂-TPD desorption patterns illustrate that Fe₂O₃/CeO₂ can adsorb and desorb C₂H₄ and SO₂ more easily than can Fe₂O₃/γ-Al₂O₃. Moreover, the SO₂-TPD patterns further show that Fe₂O₃/γ-Al₂O₃ is more seriously inhibited by SO₂. These findings may properly explain why Fe₂O₃/CeO₂ has a higher activity for the reduction of SO₂.     

SO2 resistant antimony promoted V2O5/TiO2 catalyst for NH3-SCR of NOx at low temperatures

To get the low temperature sulfur resistant V₂O₅/TiO₂ catalysts quantum chemical calculation study was carried out. After selecting suitable promoters (Se, Sb, Cu, S, B, Bi, Pb and P), respective metal promoted V₂O₅/TiO₂ catalysts were prepared by impregnation method and characterized by X-ray diffraction (XRD) and Brunner Emmett Teller surface area (BET-SA). Se, Sb, Cu, S promoted V₂O₅/TiO₂ catalysts showed high catalytic activity for NH₃ selective catalytic reduction (NH₃-SCR) of NO_x carried at temperatures between 150 and 400 °C. The conversion efficiency followed in the order of Se > Sb > S > V₂O₅/TiO₂ > Cu but Se was excluded because of its high vapor pressure. An optimal 2 wt% ‘Sb’ loading was found over V₂O₅/TiO₂ for maximum NO_x conversion, which also showed high resistance to SO₂ in presence of water when compared to other metal promoters. In situ electrical conductivity measurement was carried out for Sb(2%)/V₂O₅/TiO₂ and compared with commercial W(10%)V₂O₅/TiO₂ catalyst. High electrical conductivity difference (ΔG) for Sb(2%)/V₂O₅/TiO₂ catalyst with temperature was observed. SO₂ deactivation experiments were carried out for Sb(2%)/V₂O₅/TiO₂ and W(10%)/V₂O₅/TiO₂ at a temperature of 230 °C for 90 h, resulted Sb(2%)/V₂O₅/TiO₂ was efficient catalyst. BET-SA, X-ray photoelectron spectroscopy (XPS) and carbon, hydrogen, nitrogen and sulfur (CHNS) elemental analysis of spent catalysts well proved the presence of high ammonium sulfate salts over W(10%)/V₂O₅/TiO₂ than Sb(2%)/V₂O₅/TiO₂ catalyst.     

Effect of phosphorus addition on the hydrotreating activity of NiMo/Al2O3 carbide catalyst

A series of phosphorus promoted γ-Al₂O₃ supported NiMo carbide catalysts with 0–4.5 wt.% P, 13 wt.% Mo and 2.5 wt.% Ni were synthesized and characterized by elemental analysis, pulsed CO chemisorption, BET surface area measurement, X-ray diffraction, near-edge X-ray absorption fine structure, DRIFT spectroscopy of CO adsorption and H₂ temperature programmed reduction. X-ray diffraction patterns and CO uptake showed the P addition to NiMo/γ-Al₂O₃ carbide, increased the dispersion of β-Mo₂C particles. DRIFT spectra of adsorbed CO revealed that P addition to NiMo/γ-Al₂O₃ carbide catalyst not only increases the dispersion of Ni-Mo carbide phase, but also changes the nature of surface active sites. The hydrodenitrogenation (HDN) and hydrodesulfurization (HDS) activities of these P promoted NiMo/γ-Al₂O₃ carbide catalysts were performed in trickle bed reactor using light gas oil (LGO) derived from Athabasca bitumen and model feed containing quinoline and dibenzothiophene at industrial conditions. The P added NiMo/γ-Al₂O₃ carbide catalysts showed enhanced HDN activity compared to the NiMo/γ-Al₂O₃ catalysts with both the feed stocks. The P had almost no influence on the HDS activity of NiMo/γ-Al₂O₃ carbide with LGO and dibenzothiophene. P addition to NiMo/γ-Al₂O₃ carbide accelerated CN bond breaking and thus increased the HDN activity.     

Development of a transient kinetic model for the CO oxidation by O2 over a Pt/Rh/CeO2/γ-Al2O3 three-way catalyst

A transient kinetic model was developed for the CO oxidation by O₂ over a Pt/Rh/CeO₂/γ-Al₂O₃ three-way catalyst. The experiments which were modelled consisted of periodically switching between a feed stream containing 0.5 mol% CO in helium and a feed stream containing 0.5 mol% O₂ in helium, with a frequency from 0.1 to 0.25 Hz, in the temperature range 393–433 K. These temperatures are representative for cold start conditions. The transient experiments yield information about the reaction mechanism. A transient kinetic model based on elementary reaction steps was developed which describes the experimental data in the above mentioned range of experimental conditions adequately. The kinetic model consists of two monofunctional and one bifunctional contribution. The first monofunctional reaction path comprises competitive adsorption of CO and O₂ on the noble metal surface followed by a surface reaction. The second monofunctional reaction path consists of CO adsorption on an oxygen atom adsorbed on the noble metal surface, followed by a reaction to CO₂. The bifunctional reaction path involves a reaction between CO adsorbed on the noble metal surface and oxygen from ceria at the noble metal/ceria interface. Also, reversible adsorption of carbon dioxide on the support is taken into account. The kinetic parameters, i.e. preexponential factors and activation energies for the different elementary reaction steps, and the oxygen storage capacity were estimated using multi-response non-linear regression analysis of the oxygen, carbon monoxide and carbon dioxide outlet concentrations.     

Deactivation and regeneration of hybrid catalysts in the single-step synthesis of dimethyl ether from syngas and CO2

Synthesis of dimethyl ether (DME) has been studied in a single reaction step, from H₂ + CO and H₂ + CO₂, in a fixed bed reactor on CuO-ZnO-Al₂O₃/γ-Al₂O₃ and CuO-ZnO-Al₂O₃/NaHZSM-5 hybrid catalysts. It has been proven that water content in the reaction medium (which is higher when CO₂ is fed) contributes to efficiently decreasing deactivation by coke in both catalysts and, consequently, when water is in the feed deactivation is insignificant for 30 h reaction. Nevertheless, water also decreases the activity of γ-Al₂O₃ acid function, due to its high adsorption capacity on the acid sites. Due to its importance in the viability of the industrial process, a study has been carried on the regeneration of both catalysts by coke combustion under controlled conditions (in order to avoid CuO sintering). For this study, the catalysts have been used under severe deactivation conditions. It has been proven that γ-Al₂O₃ does not have a suitable hydrothermal stability and that CuO-ZnO-Al₂O₃/NaHZSM-5 catalyst has an excellent performance and is suitable for using it in uninterrupted reaction–regeneration cycles.     

NO reduction by CH4 in the presence of O2 over La2O3 supported on Al2O3

Dispersing La₂O₃ on δ- or γ-Al₂O₃ significantly enhances the rate of NO reduction by CH₄ in 1% O₂, compared to unsupported La₂O₃. Typically, no bend-over in activity occurs between 500° and 700°C, and the rate at 700°C is 60% higher than that with a Co/ZSM-5 catalyst. The final activity was dependent upon the La₂O₃ precursor used, the pretreatment, and the La₂O₃ loading. The most active family of catalysts consisted of La₂O₃ on γ-Al₂O₃ prepared with lanthanum acetate and calcined at 750°C for 10 h. A maximum in rate (mol/s/g) and specific activity (mol/s/m²) occurred between the addition of one and two theoretical monolayers of La₂O₃ on the γ-Al₂O₃ surface. The best catalyst, 40% La₂O₃/γ-Al₂O₃, had a turnover frequency at 700°C of 0.05 s⁻¹, based on NO chemisorption at 25°C, which was 15 times higher than that for Co/ZSM-5. These La₂O₃/Al₂O₃ catalysts exhibited stable activity under high conversion conditions as well as high CH₄ selectivity (CH₄ + NO vs. CH₄ + O₂). The addition of Sr to a 20% La₂O₃/γ-Al₂O₃ sample increased activity, and a maximum rate enhancement of 45% was obtained at a SrO loading of 5%. In contrast, addition of SO⁼₄ to the latter Sr-promoted La₂O₃/Al₂O₃ catalyst decreased activity although sulfate increased the activity of Sr-promoted La₂O₃. Dispersing La₂O₃ on SiO₂ produced catalysts with extremely low specific activities, and rates were even lower than with pure La₂O₃. This is presumably due to water sensitivity and silicate formation. The La₂O₃/Al₂O₃ catalysts are anticipated to show sufficient hydrothermal stability to allow their use in certain high-temperature applications.     

Design of a novel bifunctional catalyst IrFe/Al2O3 for preferential CO oxidation

In this study, a novel bifunctional catalyst IrFe/Al₂O₃, which is very active and selective for preferential oxidation of CO under H₂-rich atmosphere, has been developed. When the molar ratio of Fe/Ir was 5/1, the IrFe/Al₂O₃ catalyst performed best, with CO conversion of 68% and oxygen selectivity towards CO₂ formation of 86.8% attained at 100 °C. It has also been found that the impregnation sequence of Ir and Fe species on the Al₂O₃ support had a remarkable effect on the catalytic performance; the activity decreased following the order of IrFe/Al₂O₃ > co-IrFe/Al₂O₃ > FeIr/Al₂O₃. The three catalysts were characterized by XRD, H₂-TPR, FT-IR and microcalorimetry. The results demonstrated that when Ir was supported on the pre-formed Fe/Al₂O₃, the resulting structure (IrFe/Al₂O₃) allowed more metallic Ir sites exposed on the surface and accessible for CO adsorption, while did not interfere with the O₂ activation on the FeO_x species. Thus, a bifunctional catalytic mechanism has been proposed where CO adsorbed on Ir sites and O₂ adsorbed on FeO_x sites; the reaction may take place at the interface of Ir and FeO_x or via a spill-over process.     

Optimal promotion by rubidium of the CO + NO reaction over Pt/γ-Al2O3 catalysts

The reduction of NO by CO over Rb-promoted Pt/γ-Al₂O₃ catalysts has been investigated over a wide range of temperature (ca. 200–500°C), partial pressures of reactants and promoter loadings. For purposes of comparison, K- and Cs-promoted Pt/γ-Al₂O₃ catalysts were tested under the same conditions. Rubidium strongly enhanced both catalytic activity and N₂-selectivity. Rate increases by factors as high as 110 and 45 for the production of N₂ and CO₂, respectively, relative to unpromoted Pt were obtained, accompanied by substantial increase in N₂-selectivity (e.g. from 24 to 82% at 350°C and [CO]=0.5%, [NO]=1%). Under stoichiometric conditions, Rb-promoted catalysts gave 100% conversion of both reactants with 100% selectivity towards N₂ at T350°C and at an effective reactant contact time of only 0.5 s. In contrast, under the same conditions unpromoted Pt delivered <30% conversion and poor N₂-selectivity (approximately <40%); even at 480°C the conversion was only 60%. The observed promotional effects are ascribed to alkali-induced changes in the chemisorption bond strengths of CO, NO and NO dissociation products which lead to the observed activity enhancement and dependence of N₂-selectivity on promoter loading. The effects of K-promotion mirror those of Rb-promotion, but are significantly less pronounced. Rb is the best alkali promoter.     

An investigation of NO/CO reaction over perovskite-type oxide La0.8Ce0.2B0.4Mn0.6O3 (B = Cu or Ag) catalysts synthesized by reverse microemulsion

The perovskite-type oxides La_0.8Ce_0.2Cu_0.4Mn_0.6O₃ and La_0.8Ce_0.2Ag_0.4Mn_0.6O₃ prepared by reverse microemulsion and sol–gel methods (denoted as R and S, respectively), have been investigated on their catalytic performance for the (NO + CO) reaction, and characterized by means of temperature-programmed desorption (TPD), X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). XRD measurements proved the presence of the perovskite phase with a considerable amount of CeO₂ phase and the formation of CeO₂ phase was restrained with the reverse microemulsion method. TEM investigations revealed that the La_0.8Ce_0.2Cu_0.4Mn_0.6O₃-R nanoparticles were uniform spheres in shape with diameters ranging from 40 to 50 nm, whereas an aggregation of particles was found for the La_0.8Ce_0.2Cu_0.4Mn_0.6O₃-S catalyst. The activity of NO reduction with CO decreased in the order of La_0.8Ce_0.2Cu_0.4Mn_0.6O₃-R > La_0.8Ce_0.2Cu_0.4Mn_0.6O₃-S > La_0.8Ce_0.2Ag_0.4Mn_0.6O₃-R > La_0.8Ce_0.2Ag_0.4Mn_0.6O₃-S. In NO-TPD experiments, the principal desorbed species detected in the effluent was NO with a trace amount of O₂ and N₂O, suggesting that the non-dissociated adsorption of NO on the surface of the perovskite-type oxides was dominant. The XPS results revealed that Ce⁴⁺ and Cu⁺ was the predominant oxidation state for Ce and Cu components in La_0.8Ce_0.2Cu_0.4Mn_0.6O₃ and La_0.8Ce_0.2Ag_0.4Mn_0.6O₃ catalysts. The existence of Cu⁺ ions and its redox reaction (Cu⁺ ↔ Cu²⁺) would benefit the NO adsorption and reduction by CO.     

The role of lanthana loading on the catalytic properties of Pd/Al2O3-La2O3 in the NO reduction with H2

The role of La₂O₃ loading in Pd/Al₂O₃-La₂O₃ prepared by sol–gel on the catalytic properties in the NO reduction with H₂ was studied. The catalysts were characterized by N₂ physisorption, temperature-programmed reduction, differential thermal analysis, temperature-programmed oxidation and temperature-programmed desorption of NO.

The physicochemical properties of Pd catalysts as well as the catalytic activity and selectivity are modified by La₂O₃ inclusion. The selectivity depends on the NO/H₂ molar ratio (GHSV = 72,000 h⁻¹) and the extent of interaction between Pd and La₂O₃. At NO/H₂ = 0.5, the catalysts show high N₂ selectivity (60–75%) at temperatures lower than 250 °C. For NO/H₂ = 1, the N₂ selectivity is almost 100% mainly for high temperatures, and even in the presence of 10% H₂O vapor. The high N₂ selectivity indicates a high capability of the catalysts to dissociate NO upon adsorption. This property is attributed to the creation of new adsorption sites through the formation of a surface PdO_x phase interacting with La₂O₃. The formation of this phase is favored by the spreading of PdO promoted by La₂O₃. DTA shows that the phase transformation takes place at temperatures of 280–350 °C, while TPO indicates that this phase transformation is related to the oxidation process of PdO: in the case of Pd/Al₂O₃ the O₂ uptake is consistent with the oxidation of PdO to PdO₂, and when La₂O₃ is present the O₂ uptake exceeds that amount (1.5 times). La₂O₃ in Pd catalysts promotes also the oxidation of Pd and dissociative adsorption of NO mainly at low temperatures (<250 °C) favoring the formation of N₂.     

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.     

Catalytic behavior of La–Sr–Ce–Fe–O mixed oxidic/perovskitic systems for the NO+CO and NO+CH4+O2 (lean-NOx) reactions

Mixed oxides of the general formula La_0.5Sr_xCe_yFeO_z were prepared by using the nitrate method and characterized by XRD and Mössbauer techniques. The crystal phases detected were perovskites LaFeO₃ and SrFeO_3−x and oxides -Fe₂O₃ and CeO₂ depending on x and y values. The low surface area ceramic materials have been tested for the NO+CO and NO+CH₄+O₂ (“lean-NO_x”) reactions in the temperature range 250–550°C. A noticeable enhancement in NO conversion was achieved by the substitution of La³⁺ cation at A-site with divalent Sr⁺² and tetravalent Ce⁺⁴ cations. Comparison of the activity of the present and other perovskite-type materials has pointed out that the ability of the La_0.5Sr_xCe_yFeO_z materials to reduce NO by CO or by CH₄ under “lean-NO_x” conditions is very satisfying. In particular, for the NO+CO reaction estimation of turnover frequencies (TOFs, s⁻¹) at 300°C (based on NO chemisorption) revealed values comparable to Rh/-Al₂O₃ catalyst. This is an important result considering the current tendency for replacing the very active but expensive Rh and Pt metals. It was found that there is a direct correlation between the percentage of crystal phases containing iron in La_0.5Sr_xCe_yFeO_z solids and their catalytic activity. O₂ TPD (temperature-programmed desorption) and NO TPD studies confirmed that the catalytic activity for both tested reactions is related to the defect positions in the lattice of the catalysts (e.g., oxygen vacancies, cationic defects). Additionally, a remarkable oscillatory behavior during O₂ TPD studies was observed for the La_0.5Sr_0.2Ce_0.3FeO_z and La_0.5Sr_0.5FeO_z solids.     

Deactivation studies over NiO/γ-Al2O3 catalysts for partial oxidation of methane to syngas

Two types of NiO/γ-Al₂O₃ catalysts prepared by the impregnation and the sol–gel method were used for the partial oxidation of methane to syngas at 850°C (GHSV1.8×10⁵ lkg⁻¹ h⁻¹). The effects of the carbon deposition, the loss and sintering of nickel and the phase transformation of γ-Al₂O₃ support on the catalytic performance during 80 h POM reaction were investigated with a series of characterization such as XRD, BET, AAS, TG, and XPS. The results indicated that the carbon deposition and the loss and sintering of nickel could not cause the serious decrease of catalytic performance over NiO/γ-Al₂O₃ catalyst during the short-time reaction. However, the slow process of the support γ-Al₂O₃ phase transforming into -Al₂O₃ could slowly decrease the performance of NiO/γ-Al₂O₃ catalysts. Aimed at the reasons of the deactivation, an improved catalyst was obtained by the complexing agent-assisted sol–gel method.     

Re-investigating the CO oxidation mechanism over unsupported MnO, Mn2O3 and MnO2 catalysts

Kinetic study of CO oxidation in combination with experiments of temperature-programmed oxidation (TPO) and reduction (TPR) have been performed on various unsupported crystalline manganese oxides (MnO_x); while the reactivity shows an order of MnO ≤ MnO₂ < Mn₂O₃ in a mixture of unit ratio of O₂/CO at/below 523 K. We propose that under the current conditions the interaction of adsorbed CO and O is mainly responsible for CO₂ formation on Mn₂O₃ and MnO₂ catalysts, following either the Langmuir–Hinshelwood mechanism or Eley–Rideal mechanism. Meanwhile, direct evidence from transient CO oxidation suggests that the Mars-van-Krevelen mechanism may occur for all catalysts simultaneously, especially, it is predominant for the MnO catalyst. The evidence of structural modifications during reaction was confirmed by Raman spectra obtained from used MnO.