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.     

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.     

介孔LaCoO_3催化剂的制备及其光催化性能

以SBA-15为模板剂,采用纳米铸型法制备具有高比表面积的有序介孔钙钛矿型氧化物LaCoO_3催化剂,通过XRD、N2吸附-脱附和H2-TPR等对催化剂进行表征,并与溶胶-凝胶法制备的LaCoO_3催化剂比较,研究其光催化降解亚甲基蓝的性能。结果表明,纳米铸型法制备的立方晶系钙钛矿型LaCoO_3催化剂的比表面积为84 m2·g-1,对100 mg·L-1亚甲基蓝降解率达71.60%,远优于溶胶-凝胶法制备的LaCoO_3催化剂。     

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.     

Kinetic investigation of the NO reduction by H2 over noble metal based catalysts

This paper reports a kinetic investigation of the overall reduction of NO by H₂ over supported palladium based catalysts. Drastic changes in the kinetic features of Pd were found after deposition on reducible LaCoO₃ materials in comparison with alumina. Peculiar interactions between palladium and LaCoO₃ build up during a pre-activation thermal treatment in H₂ at high temperature which completely modify the kinetic behaviour of Pd. In such a case, a classical Langmuir–Hinshelwood mechanism, previously proposed on Pd/Al₂O₃, is unable to model steady-state rate measurements on pre-reduced Pd/LaCoO₃. A bi-functional mechanism involving anionic vacancies at the vicinity of palladium particles leads to a better agreement.     

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.     

Hydrodechlorination and hydrogenation of aromatic compounds over palladium on alumina in hydrogen-saturated water

The catalytic transformations of 1,2-dichlorobenzene, chlorobenzene, 4-chlorobiphenyl, γ-hexachlorocyclohexane (Lindane), naphthalene and phenanthrene were studied over palladium on alumina in hydrogen-saturated water (Pd/Al₂O₃/H₂) at room temperature and ambient pressure. The chlorinated benzenes were rapidly hydrodechlorinated and Lindane was dehydrochlorinated to benzene. Partial or complete hydrogenation was observed for biphenyl and the polycyclic aromatic hydrocarbons. The phenanthrene ring was cleaved at the 9,10-position. In general dechlorination reactions were faster than hydrogenation reactions.     

Total Oxidation of Methane and Chlorinated Hydrocarbons on Zirconia Supported A1–xSrxMnO3 Catalysts

The catalytic behavior of ZrO₂ and ZrO₂ containing 8 mol‐% Y₂O₃ supported A_1–xSr_xMnO₃ (A = La, didymium) perovskites was studied in the total oxidation of methane, chloromethane and dichloromethane considering catalyst deactivation and byproduct formation. The perovskites are dispersed on the support surface; clusters with a perovskite‐like structure were formed. The supported catalysts are characterized by higher specific surface areas compared with the unsupported ones. Partial substitution of A‐site cations by Sr leads to an enhancement of the catalytic activity in the total oxidation of methane, but not in the total oxidation of chlorinated hydrocarbons (CHC). The catalytic activity of supported and unsupported catalysts is comparable in the total oxidation of methane in spite of the significantly lower perovskite content of the supported catalysts. In the CHC conversion the catalytic activity of the supported catalysts is higher than that of the unsupported ones.     

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.     

An in situ study of the NO + H2 + O2 reaction on Pd/LaCoO3 based catalysts

In situ X-ray diffraction (XRD) and quasi in situ X-ray photoelectron spectroscopy (XPS) measurements were complementary used to investigate structural and surface modifications of a palladium-supported on LaCoO₃ perovskite catalyst under various controlled atmospheres, particularly during the reduction of NO by hydrogen under lean conditions, in the presence of a large excess of oxygen.

An extensive reduction of the perovskite was evidenced during the pre-activation thermal treatment of the palladium-supported catalyst under hydrogen at 773 K leading to the formation of Pd particles in contact with Co⁰ and La₂O₃. In the presence of an excess of oxygen, the catalyst structure changes during the reaction. The reduced solid is progressively transformed into LaCoO₃ in the range of 873–1173 K. However, such a bulk transformation probably occurs at lower temperatures at the surface of the solid according to XPS analyses. At the same time, the binding energy (BE) level of the Pd 3d_5/2 photopeak increases up to 337.5 eV which reveals the stabilisation of oxidic palladium species in a different chemical environment than that corresponding to PdO. Such changes induced different catalytic properties of the catalyst during the reduction of NO by H₂.     

Kinetics of the NO + H2 reaction over supported noble metal based catalysts: Support effect on their adsorption properties

This paper reports a kinetic investigation of the global reduction of NO by H₂ which has been considered as a probe reaction for characterising the adsorption properties of supported palladium based catalysts. A particular attention has been paid towards the influence of the support on the catalytic properties of Pd, particularly towards the production of undesirable by-products such as nitrous oxide (N₂O) and ammonia (NH₃). It has been found that the kinetics of the overall NO + H₂ reaction on Pd/Al₂O₃ can be correctly depicted according to a Langmuir–Hinshelwood mechanism involving the dissociation of nitrosyl species assisted by chemisorbed hydrogen atoms. On the other hand, Pd/LaCoO₃ exhibits a different kinetic behaviour towards the adsorption of hydrogen depending on the pre-activation thermal treatment. In that case, different mechanisms may occur.     

On the role of gallium for the aromatization of lower paraffins with Ga-promoted ZSM-5 catalysts

Aromatization of butane or propane was conducted with a series of ZSM-5 catalysts. A small amount of oxygen in the feed promoted butane conversion to aromatic hydrocarbons on H-ZSM-5. It suggests that if hydrogen atoms on the zeolite surface are removed effectively, H-ZSM-5 exhibits a high selectivity for aromatic hydrocarbons. A hybrid catalyst composed of the physical mixture of Ga/SiO₂ and H-ZSM-5 showed comparable activity and aromatic selectivity to those of the Ga-supported ZSM-5 zeolite, whereas the Ga/SiO₂ itself exhibited little catalytic activity for the paraffin conversion and olefin aromatization. The excellent promotional effect of Ga/SiO₂for aromatics formation was observed only when it was intimately contacted with H-ZSM-5. These results suggest that the supported Ga promotes the zeolite-catalyzed aromatization of lower paraffins by promoting hydrogen desorption via the ‘reverse spillover’ effects.     

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.     

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.     

LaCoO3钙钛矿活化过一硫酸盐降解萘普生

在催化活化过一硫酸盐(PMS)降解水中污染物的反应中,通过添加钴基钙钛矿提高反应效率。利用溶胶凝胶法制备了LaCoO₃钙钛矿,通过实验评估LaCoO₃/PMS体系对非甾体抗炎药萘普生（NAP）的降解效果。分析了LaCoO₃投加量、PMS投加量、反应初始pH、Cl^-浓度和腐殖酸（HA）对NAP去除率的影响以及该体系的矿化能力。结果表明NAP降解的反应速率随LaCoO₃和PMS投加量增加而增大;反应初始pH在5.0时NAP降解效果最好;溶液中存在Cl^-对降解有促进效果,且Cl^-浓度越大促进效果越明显;腐殖酸（HA）对反应有一定程度的抑制效果;LaCoO₃在重复利用5次时仍有较好的稳定性。此外,自由基淬灭实验结果表明在LaCoO₃/PMS体系中SO₄^·-为主要活性物质。     

Au/LaCo_(1-x)Ce_xO_3催化剂的制备及其对CO催化氧化性能的研究

为进一步提高催化剂活性,用Ce对LaCoO3载体进行改性,并采用溶胶-凝胶法制备系列LaCo1-xCexO3(x=0~0.5)载体。其中,x=0.1和0.2时,载体为钙钛矿结构。采用沉积-沉淀法制备Au/LaCo1-xCexO3(x=0.1、0.2)催化剂,通过XRD、BET和H2-TPR等方法对催化剂进行催化活性评价及稳定性表征测试。结果表明,Au/LaCo0.9Ce0.1O3和Au/LaCo0.8Ce0.2O3催化剂能够在90℃将CO完全转化,在此温度进行的连续20h和30h的寿命实验中,CO转化率保持100%,催化活性和稳定性均优于Au/LaCoO3催化剂。表明掺杂Ce改性载体,能够提高催化剂活性和稳定性。     

Production of aromatic hydrocarbons by co-cracking of bio-oil and ethanol over Ga2O3/HZSM-5 catalysts

The catalytic cracking of bio-oil is important to produce aromatic hydrocarbons, which can partially replace gasoline or diesel to greatly reduce carbon emissions from transportation. To further promote the formation of aromatic hydrocarbons, this work studied the effects of the preparation method and the acid strength of Ga₂O₃/HZSM-5 on catalytic cracking of the bio-oil distilled fraction systematically. The preparation method of Ga₂O₃/HZSM-5 had an important effect on its catalytic activity: the Ga₂O₃/HZSM-5 prepared by physical mixing showed the low dispersion of active phases and poor pore structure, resulting in its insufficient activity and severe coke deposition; the Ga₂O₃/HZSM-5 prepared by precipitation exhibited the higher activity, while many polycyclic aromatic hydrocarbons unfavorable for the subsequent utilization were in the oil phase; the Ga₂O₃/HZSM-5 prepared by impregnation showed the highest activity and 35.5% (mass) selectivity of the oil phase, including 80.3% monocyclic aromatic hydrocarbons and 12.0% polycyclic aromatic hydrocarbons. The Brønsted acidity of Ga₂O₃/HZSM-5 decreased with Si/Al ratio, leading to the decline in reactant conversion, oil phase selectivity and quality. Meanwhile, the polymerization between monocyclic aromatic hydrocarbons and oxygenates was promoted to produce many polycyclic aromatic hydrocarbons and even coke, causing catalyst deactivation.     

Fuel-rich catalytic combustion of methane in zero emissions power generation processes

A novel catalytic combustion concept for zero emissions power generation has been investigated. Catalysts consisting of Rh supported on ZrO₂, Ce-ZrO₂ or -Al₂O₃ were prepared and tested under fuel-rich conditions, i.e. for catalytic partial oxidation (CPO) of methane. The experiments were performed in a subscale gas-turbine reactor operating at 5 bar with exhaust gas-diluted feed mixtures.

The catalyst support material was found to influence the light-off temperature significantly, which increased in the following order Rh/Ce-ZrO₂ < Rh/ZrO₂ < Rh/-Al₂O₃. The Rh loading, however, only had a minor influence. The high activity of Rh/Ce-ZrO₂ is probably related to the high dispersion of Rh on Ce-ZrO₂ and the high oxygen mobility of this support compared to pure ZrO₂. The formation of hydrogen was also found to increase over the catalyst containing ceria in the support material.     

NiO-LaCoO3催化剂的丙烷和CO氧化性能

采用固相反应制备了NiO-LaCoO₃催化剂,考察了焙烧温度以及Ni含量对催化剂的CO和丙烷氧化活性的影响。用X射线粉末衍射、H₂-程序升温还原等技术对催化剂进行了表征。结果表明,在焙烧温度为700~1000℃时,焙烧温度越高,催化剂的丙烷和CO氧化性能越差,其中700℃焙烧后的10NiO-LaCoO₃催化剂的效果最好。助剂Ni能有效提高LaCoO₃催化剂的丙烷和CO氧化性能,其中Ni含量为7.5%的7.5NiO-LaCoO₃催化剂氧化性能最佳。研究发现催化剂的CO和丙烷氧化活性与催化剂中氧活动性具有相关性。     

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.