Palladium-substituted lanthanum cuprates: application to automotive exhaust purification

A series of palladium-substituted La₂CuO₄, corresponding to the formula La₂Cu_{1 −x}Pd_xO₄ (x = 0−0.2) were prepared by metal nitrate decomposition in a polyacrylamide gel. This method allows an easy incorporation of palladium in the mixed-oxides, which are formed at moderate temperature with rather high specific areas (13–17 m²/g). The partial substitution of copper for palladium allows a strong improvement of the three-way catalytic activity, in particular for NO reduction. The light-off temperatures for the conversions of CO, NO and C₃H₆ decreased markedly when increasing the palladium content, the activity of catalysts La₂Cu_0.9Pd_0.1O₄ and La₂Cu_0.8Pd_0.2O₄ being comparable to that of a Pt-Rh/CeO₂–Al₂O₃ catalyst for NO reduction, and higher for CO and C₃H₆ oxidation.

All the La₂Cu_{1 − x} Pd_xO₄ catalysts are activated under reacting conditions. This activation corresponds to the destruction of the mixed-oxide structure, with formation of reduced Pd⁰ ions atomically dispersed, surrounded by Cu⁺ and Cu²⁺ species on a lanthanum oxycarbonate matrix. This high dispersion state of the two transition metals in various oxidation states is supposed to originate from the initial La₂Cu_{1 −x}Pd_xO₄ structure.     

火焰喷雾合成法制备La0.8Sr0.2Mn1-xCuxO3催化氧化CO性能研究

采用火焰喷雾合成法制备了Sr²⁺、Cu²⁺分别取代A、B位的La_0.8Sr_0.2Mn_1-xCu_xO₃ （x=0,0.1,0.2,0.3,0.4）钙钛矿催化剂,并用于CO催化氧化实验,研究了水蒸气和CO₂对催化剂CO氧化活性的影响。对不同取代量La_0.8Sr_0.2Mn_1-xCu_xO₃ 催化剂进行了XRD、SEM、EDS、BET、XPS、H₂-TPR和O₂-TPD等表征测试。结果表明,火焰喷雾合成法制备的钙钛矿催化剂具有良好的钙钛矿相、疏松多孔结构和催化氧化活性。其中,La_0.8Sr_0.2Mn_0.9Cu_0.1O₃分别在119.4℃和133.3℃实现50%和90%的CO转化率。掺杂水蒸气和CO₂会与CO在催化剂表面形成竞争吸附,导致5种催化剂性能衰减,但La_0.8Sr_0.2Mn_0.9Cu_0.1O₃仍能在150.2℃实现90%的CO催化转化,在连续稳定性催化氧化测试中,5种催化剂性能衰减不超过10%。结合上述CO催化氧化实验,火焰喷雾合成法制备的催化剂具有良好的稳定性和催化活性,适合制备高CO催化氧化活性的钙钛矿催化剂。     

Decomposition of nitric oxide over perovskite oxide catalysts: effect of CO2, H2O and CH4

Direct nitric oxide decomposition over perovskites is fairly slow and complex, its mechanism changing dramatically with temperature. Previous kinetic study for three representative compositions (La_0.87Sr_0.13Mn_0.2Ni_0.8O_3−δ, La_0.66Sr_0.34Ni_0.3Co_0.7O_3−δ and La_0.8Sr_0.2Cu_0.15Fe_0.85O_3−δ) has shown that depending on the temperature range, the inhibition effect of oxygen either increases or decreases with temperature. This paper deals with the effect of CO₂, H₂O and CH₄ on the nitric oxide decomposition over the same perovskites studied at a steady-state in a plug-flow reactor with 1 g catalyst and total flowrates of 50 or 100 ml/min of 2 or 5% NO. The effect of carbon dioxide (0.5–10%) was evaluated between 873 and 923 K, whereas that of H₂O vapor (1.6 or 2.5%) from 723 to 923 K. Both CO₂ and H₂O inhibit the NO decomposition, but inhibition by CO₂ is considerably stronger. For all three catalysts, these effects increase with temperature. Kinetic parameters for the inhibiting effects of CO₂ and H₂O over the three perovskites were determined. Addition of methane to the feed (NO/CH₄=4) increases conversion of NO to N₂ about two to four times, depending on the initial NO concentration and on temperature. This, however, is still much too low for practical applications. Furthermore, the rates of methane oxidation by nitric oxide over perovskites are substantially slower than those of methane oxidation by oxygen. Thus, perovskites do not seem to be suitable for catalytic selective NO reduction with methane.     

Study of Ag/La0.6Sr0.4MnO3 catalysts for complete oxidation of methanol and ethanol at low concentrations

Ag-modified La_0.6Sr_0.4MnO₃-based catalysts with the perovskite-type structure were prepared by using a citric acid sol–gel method, and their catalytic performance for complete oxidation of methanol and ethanol was evaluated and compared with that of the γ-Al₂O₃-supported catalysts, Ag/γ-Al₂O₃, Pt/γ-Al₂O₃, and Pd/γ-Al₂O₃. The results showed that the Ag-modified La_0.6Sr_0.4MnO₃-based catalysts with the perovskite-type structure displayed the activity significantly higher than that of the supported precious metal catalysts, 0.1%Pd/γ-Al₂O₃ and 0.1%Pt/γ-Al₂O₃ in the temperature range of 370–573 K. Over a 6%Ag/20%La_0.6Sr_0.4MnO₃/γ-Al₂O₃ catalyst, the T₉₅ temperature for methanol oxidation can be as low as 413 K. Even at such low reaction temperature, there were little HCHO and CO detected in the reaction exit-gas. However, for the 0.1%Pd/γ-Al₂O₃ and 0.1%Pt/γ-Al₂O₃ catalysts, the HCHO content in the reaction exit-gas reached 200 and 630 ppm at their T₉₅ temperatures. Over a 6%Ag/La_0.6Sr_0.4MnO₃ catalyst, the T₉₅ temperature for ethanol oxidation can be as low as 453 K, with a corresponding content of CH₃CHO in the exit-gas at 782 ppm; when ethanol oxidation is performed at 493 K, the content of acetaldehyde in the exit-gas can be below 1 ppm. Characterization of the catalysts by X-ray diffraction (XRD), TEM, XPS, laser Raman spectra (LRS), hydrogen temperature-programmed reduction (H₂-TPR) and oxygen temperature-programmed desorption (O₂-TPD) methods revealed that both the surface and the bulk phase of the perovskite La_0.6Sr_0.4MnO₃ played important roles in the catalytic oxidation of the alcohols, and that γ-Al₂O₃ as the bottom carrier could be beneficial in creating a large surface area of catalyst. Moreover, a small amount of Ag⁺ doped onto the surface of La_0.6Sr_0.4MnO₃ was able to partially occupy the positions of La³⁺ and Sr²⁺ due to their similar ionic radii, and thus, became stabilized by the perovskite lattice, which would be in favor of preventing the aggregation of the Ag species on the surface and enhancing the stability of the catalyst. On the other hand, modification of the Ag⁺ to the surface of La_0.6Sr_0.4MnO₃ resulted in an increase in relative content of the surface O₂²⁻/O⁻ species highly reactive toward the alcohols and aldehydes as well as CO. Besides, solution of low-valence metal oxides SrO and Ag₂O with proper amounts in the lattice of the trivalent metal perovskite-type oxide LaMnO₃ would also lead to an increase in the content of the reducible Mnⁿ⁺ and the formation of anionic vacancies, which would be favorable for the adsorption-activation of oxygen on the functioning catalyst and the transport of the lattice and surface oxygen species. All these factors would contribute to the pronounced improvement of the catalyst performance.     

Reduction of CeO2 in composites with transition metal complex oxides under hydrogen containing atmosphere and its correlation with catalytic activity

Reduction behavior of pure and doped CeO₂, the multi-phase La_0.6Sr_0.4CoO₃?xCeO₂, La_0.8Sr_0.2MnO₃ ?xCeO₂, and La_0.95Ni_0.6Fe_0.4O₃?xCeO₂ composites, was studied under hydrogen containing atmosphere to address issues related to the improvement of electrochemical and catalytic performance of electrodes in fuel cells. The enhanced reduction of cerium oxide was observed initially at 800°C in all composites in spite of the presence of highly reducible transition metal cations that could lead to the increase in surface concentration of oxygen vacancies and generation of the electron enriched surface. Due to continuous reduction of cerium oxide in La_0.6Sr_0.4CoO₃?xCeO₂ and La_0.8Sr_0.2MnO₃?xCeO₂ (up to 10 h) composites the redox activity of the Ce⁴⁺/Ce³⁺ pair could be suppressed and additional measures are required for reversible spontaneous regeneration of Ce⁴⁺. After 3 h exposure to H₂-Ar at 800°C the reduction of cerium oxides and perovskite phases in La_0.95Ni_0.6Fe_0.4O₃?xCeO₂ composites was diminished. The extent of cerium oxide involvement in the reduction process varies with time, and depends on its initial deviation from oxygen stoichiometry (that results in the larger lattice parameter and the longer pathway for O^2- transport through the fluorite lattice), chemical origin of transition metal cations in the perovskite, and phase diversity in multi-phase composites.     

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.     

氨分解制氢棒状LaxCe1-xOy负载Ru催化剂

氨分解得到的H₂不含CO _x 、SO _x 、NO _x 等有害物质,是其他所有含碳资源为原料制氢所不能比拟的。本文采用无模板水热法制备了一系列棒状载体,并采用沉积沉淀法制备了Ru/La _x Ce_1-x O _y 催化剂,考察了制备方法、催化剂组成对性能的影响,并通过扫描电镜（SEM）、X射线衍射（XRD）、BET、H₂-程序升温还原（TPR）和CO₂-程序升温脱附（TPD）进行了表征。结果表明,La₂O₃掺杂量为40%的Ru/La_0.4Ce_0.6O_1.8催化剂在常压、7800h^-1、450℃下氨分解转化率为98%。该催化剂活性高归因于部分还原的CeO_2-x 对Ru的供电子性能和Ru/La_0.4Ce_0.6O_1.8催化剂表面的强碱性增加了对Ru活性位的给电子能力。同时考察了K₂O含量的影响,最优的催化剂为Ru-2%K/La_0.4Ce_0.6O_1.8,在400℃、7800h^-1氨气转化率可以达到93%。结果表明Ru-2%K/La_0.4Ce_0.6O_1.8可以作为一种新型高效氨分解催化剂,为工业化应用提供了可能,具有良好的发展前景。     

复合阳极Ni-Fe/Ce0.9Gd0.1O1.95在阴极支撑单电池的性能及其表征

为了提高固体氧化物燃料电池在中温条件下的电性能,探索了一种双金属阳极的阴极支撑单电池。单电池以La_0.6Sr_0.4CoO₃（LSC）-Ce_0.9Gd_0.1O_1.95（GDC）为阴极支撑体,旋涂了甘氨酸-硝酸盐法制备的La_0.9Sr_0.1Ga_0.8Mg_0.2O_3-δ（LSGM）电解质及Sm_0.2Ce_0.8O_1.9（SDC）缓冲层,涂覆了由硬模板法和浸渍法结合制备的Ni-Fe/GDC双金属阳极。对制备材料进行了XRD和微观形貌分析,单电池电化学测试在800 ℃和750 ℃下,以氢气为燃料的最大功率密度达0.73 W/cm²和0.64 W/cm²,以甲烷为燃料时达0.41 W/cm²和0.40 W/cm²。测试后的SEM表明,阳极具有多孔的微观结构,金属颗粒均匀包覆蠕虫状GDC,保证了单电池具有较高的发电性能。     

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.     

Activation of methane using solid oxide membranes

Dense membranes of mixed-conducting perovskite-type oxides La_0.6Sr_0.4,CO_0.8Fe_0.2O₃ and La_0.8Ba_0.2Co_0.8Fe_0.2O₃ were used for methane coupling by application of pressure-driven O₂ permeation. High operating temperatures, typically above 800°C, were needed to obtain reasonable oxygen fluxes. Conversions were small (1–3%). Both compositions showed comparable C₂ selectivities at low methane partial pressures. At higher pressures the selectivity to C₂ hydrocarbons for La_0.6Sr_0.4CO_0.8Fe_0.2O₃ increased to 67%, whereas La_0.8Ba_0.2CO_0.8Fe_0.2O₃ showed small C₂ selectivities. Strong surface segregation of Sr and Ba was shown by SEM for both compositions.     

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.     

Water vapor sensitivity of nanosized La(Co, Mn, Fe)1−x(Cu, Pd)xO3 perovskites during NO reduction by C3H6 in the presence of oxygen

A series of La(Co, Mn, Fe)_1−x(Cu, Pd)_xO₃ perovskites having high specific surface areas and nanosized crystal domains was prepared by reactive grinding. The solids were characterized by N₂ adsorption, X-ray diffraction (XRD), scanning electron microscopy (SEM), temperature programmed desorption (TPD) of O₂, NO + O₂, C₃H₆, in the absence or presence of 5% H₂O, Fourier transform infrared (FTIR) spectroscopy, as well as activity tests towards NO reduction by propene under the conditions of 3000 ppm NO, 3000 ppm C₃H₆, 1% O₂, 0 or 10% H₂O, and 50,000 h⁻¹ space velocity. The objective was to investigate the influence of H₂O addition on catalytic behavior. A good performance (100% NO conversion, 77% N₂ yield, and 90% C₃H₆ conversion) was achieved at 600 °C over LaFe_0.8Cu_0.2O₃ under a dry feed stream. With the exposure of LaFe_0.8Cu_0.2O₃ to a humid atmosphere containing 10% water vapor, the catalytic activity was slightly decreased yielding 91% NO conversion, 51% N₂ yield, and 86% C₃H₆ conversion. A competitive adsorption between H₂O vapor with O₂ and NO molecules at anion vacancies over LaFe_0.8Cu_0.2O₃ was found by means of TPD studies here. A deactivation mechanism was therefore proposed involving the occupation of available active sites by water vapor, resulting in an inhibition of catalytic activity in C₃H₆ + NO + O₂ reaction. This H₂O deactivation was also verified to be strictly reversible by removing steam from the feed.     

CH4/CO2 reforming over La2NiO4 and 10%NiO/CeO2–La2O3 catalysts under the condition of supersonic jet expansion via cavity ring-down spectroscopic analysis

CH₄/CO₂ reforming over La₂NiO₄ and 10%NiO/CeO₂–La₂O₃ catalysts under the condition of supersonic jet expansion was studied via direct monitoring of the reactants and products using the sensitive technique of cavity ring-down spectroscopy. Vibration–rotational absorption lines of CH₄, H₂O, CO₂ and CO molecules were recorded in the near infrared spectral region. Our results indicated that La₂NiO₄ is superior to 10%NiO/CeO₂–La₂O₃ in performance. In addition, we observed enhanced reverse-water-gas-shift reaction at augmented reaction temperature. The formation of reaction intermediates was also investigated by means of time-of-flight mass spectrometry and there was the detection of CH_x⁺, OH⁺ and H⁺ species.     

Co3O4/CeO2 composite oxides for methane emissions abatement: Relationship between Co3O4–CeO2 interaction and catalytic activity

Co₃O₄/CeO₂ composite oxides with different cobalt loading (5, 15, 30, 50, 70 wt.% as Co₃O₄) were prepared by co-precipitation method and investigated for the oxidation of methane under stoichiometric conditions. Pure oxides, Co₃O₄ and CeO₂ were used as reference. Characterization studies by X-ray diffraction (XRD), BET, temperature programmed reduction/oxidation (TPR/TPO) and X-ray photoelectron spectroscopy (XPS) were carried out.

An improvement of the catalytic activity and thermal stability of the composite oxides was observed with respect to pure Co₃O₄ in correspondence of Co₃O₄–CeO₂ containing 30% by weight of Co₃O₄. The combined effect of cobalt oxide and ceria, at this composition, strongly influences the morphological and redox properties of the composite oxides, by dispersing the Co₃O₄ phase and promoting the efficiency of the Co³⁺–Co²⁺ redox couple. The presence in the sample Co₃O₄(30 wt.%)–CeO₂ of a high relative amount of Ce³⁺/(Ce⁴⁺ + Ce³⁺) as detected by XPS confirms the enhanced oxygen mobility.

The catalysts stability under reaction conditions was investigated by XRD and XPS analysis of the used samples, paying particular attention to the Co₃O₄ phase decomposition. Methane oxidation tests were performed over fresh (as prepared) and thermal aged samples (after ageing at 750 °C for 7 h, in furnace). The resistance to water vapour poisoning was evaluated for pure Co₃O₄ and Co₃O₄(30 wt.%)–CeO₂, performing the tests in the presence of 5 vol.% H₂O. A methane oxidation test upon hydrothermal ageing (flowing at 600 °C for 16 h a mixture 5 vol.% H₂O + 5 vol.%O₂ in He) of the Co₃O₄(30 wt.%)–CeO₂ sample was also performed. All the results confirm the superiority of this composite oxide.     

AFeO3 (A=La, Nd, Sm) and LaFe1−xMgxO3 perovskites as methane combustion and CO oxidation catalysts: structural, redox and catalytic properties

Catalytic methane combustion and CO oxidation were investigated over AFeO₃ (A=La, Nd, Sm) and LaFe_1−xMg_xO₃ (x=0.1, 0.2, 0.3, 0.4, 0.5) perovskites prepared by citrate method and calcined at 1073 K. The catalysts were characterized by X-ray diffraction (XRD). Redox properties and the content of Fe⁴⁺ were derived from temperature programmed reduction (TPR). Specific surface areas (SA) of perovskites were in 2.3–9.7 m² g⁻¹ range. XRD analysis showed that LaFeO₃, NdFeO₃, SmFeO₃ and LaFe_1−xMg_xO₃ (x·0.3) are single phase perovskite-type oxides. Traces of La₂O₃, in addition to the perovskite phase, were detected in the LaFe_1−xMg_xO₃ catalysts with x=0.4 and 0.5. TPR gave evidence of the presence in AFeO₃ of a very small fraction of Fe⁴⁺ which reduces to Fe³⁺. The fraction of Fe⁴⁺ in the LaFe_1−xMg_xO₃ samples increased with increasing magnesium content up to x=0.2, then it remained nearly constant. Catalytic activity tests showed that all samples gave methane and CO complete conversion with 100% selectivity to CO₂ below 973 and 773 K, respectively. For the AFeO₃ materials the order of activity towards methane combustion is La>Nd>Sm, whereas the activity, per unit SA, of the LaFe_1−xMg_xO₃ catalysts decreases with the amount of Mg at least for the catalysts showing a single perovskite phase (x=0.3). Concerning the CO oxidation, the order of activity for the AFeO₃ materials is Nd>La>Sm, while the activity (per unit SA) of the LaFe_1−xMg_xO₃ catalysts decreases at high magnesium content.     

Catalytic reduction of NO by propene over LaCo1−xCuxO3 perovskites synthesized by reactive grinding

One series of LaCo_1−xCu_xO₃ perovskites with high specific surface area was prepared by the new method designated as reactive grinding. These solids were characterized by N₂ adsorption, X-ray diffraction (XRD), scanning electron microscopy (SEM), H₂-temperature programmed reduction (TPR), O₂-temperature programmed desorption (TPD), NO + O₂-TPD, C₃H₆-TPD, NO + O₂-temperature programmed surface reaction (TPSR) under C₃H₆/He flow as well as catalytic reduction of NO activity tests. The catalytic performance of unsubstituted sample is poor with a maximum conversion to N₂ of 19% at 500 °C at a space velocity of 55,000 h⁻¹ (3000 ppm NO, 3000 ppm C₃H₆, 1% O₂ in helium) but it is improved by incorporation of Cu into the lattice. A maximal N₂ yield of 46% was observed over LaCo_0.8Cu_0.2O₃ under the same conditions. Not only the abundance of -oxygen but also the mobility of β-oxygen of lanthanum cobaltite was remarkably enhanced by Cu substitution according to O₂-TPD and H₂-TPR studies. The better performance of Cu-substituted samples is likely to correspond to the essential nature of Cu and facility to form nitrate species in NO transformation conditions. In the absence of O₂, the reduction of NO by C₃H₆ was performed over LaCo_0.8Cu_0.2O₃, leading to a maximal conversion to N₂ of 73% accompanied with the appearance of some organo nitrogen compounds (identified as mainly C₃H₇NO₂). Subsequently, a mechanism involving the formation of an organic nitro intermediate, which further converts into N₂, CO₂ and H₂O via isocyanate, was proposed. Gaseous oxygen acts rather as an inhibitor in the reaction of NO and C₃H₆ over highly oxidative LaCo_0.8Cu_0.2O₃ due to the heavily unselective combustion of C₃H₆ by O₂.     

Catalytic reduction of NO by CO over NiO/CeO2 catalyst in stoichiometric NO/CO and NO/CO/O2 reaction

A new catalyst composed of nickel oxide and cerium oxide was studied with respect to its activity for NO reduction by CO under stoichiometric conditions in the absence as well as the presence of oxygen. Activity measurements of the NO/CO reaction were also conducted over NiO/γ-Al₂O₃, NiO/TiO₂, and NiO/CeO₂ catalysts for comparison purposes. The results showed that the conversion of NO and CO are dependent on the nature of supports, and the catalysts decreased in activity in the order of NiO/CeO₂ > NiO/γ-Al₂O₃ > NiO/TiO₂. Three kinds of CeO₂ were prepared and used as support for NiO. They are the CeO₂ prepared by (i) homogeneous precipitation (HP), (ii) precipitation (PC), and (iii) direct decomposition (DP) method. We found that the NiO/CeO₂(HP) catalyst was the most active, and complete conversion of NO and CO occurred at 210 °C at a space velocity of 120,000 h⁻¹. Based on the results of surface analysis, a reaction model for NO/CO interaction over NiO/CeO₂ has been proposed: (i) CO reduces surface oxygen to create vacant sites; (ii) on the vacant sites, NO dissociates to produce N₂; and (iii) the oxygen originated from NO dissociation is removed by CO.     

Comparative analysis of ceramic-carbonate nanocomposite fuel cells using composite GDC/NLC electrolyte with different perovskite structured cathode materials

A comparative analysis of perovskite structured cathode materials, La_0.65Sr_0.35MnO₃ (LSM), La_0.8Sr_0.2CoO₃ (LSC), La_0.6Sr_0.4FeO₃ (LSF) and La_0.6Sr_0.4Co_0.2Fe_0.8O₃ (LSCF), was performed for a ceramic-carbonate nanocomposite fuel cell using composite electrolyte consisting of Gd_0.1Ce_0.9O_1.95 (GDC) and a eutectic mixture of Na₂CO₃ and Li₂CO₃. The compatibility of these nanocomposite electrode powder materials was investigated under air, CO₂ and air/CO₂ atmospheres at 550 °C. Microscopy measurements together with energy dispersive X-ray spectroscopy (EDS) elementary analysis revealed few spots with higher counts of manganese relative to lanthanum and strontium under pure CO₂ atmosphere. Furthermore, electrochemical impedance (EIS) analysis showed that LSC had the lowest resistance to oxygen reduction reaction (ORR) (14.12 Ω·cm²) followed by LSF (15.23 Ω·cm²), LSCF (19.38 Ω·cm²) and LSM (>300 Ω·cm²). In addition, low frequency EIS measurements (down to 50 µHz) revealed two additional semi-circles at frequencies around 1 Hz. These semicircles can yield additional information about electrochemical reactions in the device. Finally, a fuel cell was fabricated using GDC/NLC nanocomposite electrolyte and its composite with NiO and LSCF as anode and cathode, respectively. The cell produced an excellent power density of 1.06 W/cm² at 550 °C under fuel cell conditions.     

The effect of oxygen concentration on the reduction of NO with propylene over CuO/γ-Al2O3

The effect of oxygen concentration on the pulse and steady-state selective catalytic reduction (SCR) of NO with C₃H₆ over CuO/γ-Al₂O₃ has been studied by infrared spectroscopy (IR) coupled with mass spectroscopy studies. IR studies revealed that the pulse SCR occurred via (i) the oxidation of Cu⁰/Cu⁺ to Cu²⁺ by NO and O₂, (ii) the co-adsorption of NO/NO₂/O₂ to produce Cu²⁺(NO₃⁻)₂, and (iii) the reaction of Cu²⁺(NO₃⁻)₂ with C₃H₆ to produce N₂, CO₂, and H₂O. Increasing the O₂/NO ratio from 25.0 to 83.4 promotes the formation of NO₂ from gas phase oxidation of NO, resulting in a reactant mixture of NO/NO₂/O₂. This reactant mixture allows the formation of Cu²⁺(NO₃⁻)₂ and its reaction with the C₃H₆ to occur at a higher rate with a higher selectivity toward N₂ than the low O₂/NO flow. Both the high and low O₂/NO steady-state SCR reactions follow the same pathway, proceeding via adsorbed C₃H₇---NO₂, C₃H₇---ONO, CH₃COO⁻, Cu⁰---CN, and Cu⁺---NCO intermediates toward N₂, CO₂, and H₂O products. High O₂ concentration in the high O₂/NO SCR accelerates both the formation and destruction of adsorbates, resulting in their intensities similar to the low O₂/NO SCR at 523–698 K. High O₂ concentration in the reactant mixture resulted in a higher rate of destruction of the intermediates than low O₂ concentration at temperatures above 723 K.     

Development of solid oxide fuel cells based on a Ce(Gd)O2−x electrolyte film for intermediate temperature operation

Initial tests have been carried out with the fuel cell arrangement La_0.6Sr_0.4Co_0.2Fe_0.8O₃Ce_0.9Gd_0.1O_1.95Ni/YSZ, incorporating dense film (5–10 μm) Ce_0.9Gd_0.1O_1.95 electrolyte tape cast onto the supporting anode, to investigate the feasibility of intermediate temperature operation (500–700°C). A good open circuit voltage of approx. 0.8 V was obtained at 550°C using moist hydrogen as the fuel. Slightly lower open circuit voltages were found at higher temperatures, which may have been caused by minor gas leakage and the electronic conductivity of the electrolyte. Power outputs in excess of 100 mW/cm² were obtained at 650°C, and the cell resistance was 0.8Ω cm² at this temperature. This resistance, and the greater resistance at lower temperature, was predominantly due to the cathode according to AC impedance measurements. Experiments were also carried out at 600°C using direct methanol fuels at the anode; the maximum power output was approximately half of that obtained with hydrogen.