Catalytic Properties of Ceria and CeO2-Containing Materials

Over the past several years, cerium oxide and CeO₂-containing materials have come under intense scrutiny as catalysts and as structural and electronic promoters of heterogeneous catalytic reactions. Recent developments regarding the characterization of ceria and CeO₂-containing catalysts are critically reviewed with a special focus towards catalyst interaction with small molecules such as hydrogen, carbon monoxide, oxygen, and nitric oxide. Relevant catalytic and technological applications such as the use of ceria in automotive exhaust emission control and in the formulation of SO_x reduction catalysts is described. A survey of the use of CeO₂-containing materials as oxidation and reduction catalysts is also presented.     

Catalytic reduction of nitrogen oxides with methane in the presence of excess oxygen

We discovered a family of catalysts that can effectively reduce NO_x with methane in the presence of excess oxygen. This new catalytic chemistry offers an alternative means for controlling NO_x emissions. Complete reduction of nitric oxide was obtained at 400°C over a Co-ZSM-5 catalyst. The presence of oxygen in the feed greatly enhances the nitric oxide reduction activity on Co-ZSM-5, and the nitric oxide conversion is strongly related to the inlet methane level. On the other hand, Cu-ZSM-5, which is a unique catalyst for the direct nitric oxide decomposition, is a poor catalyst for nitric oxide reduction by methane in the presence of excess of oxygen.     

Selective catalytic reduction of nitric oxide by ammonia on Fe-promoted active carbon

Selective catalytic reduction of nitric oxide by ammonia on Fe³⁺-promoted active carbons was investigated. The catalysts were prepared by the impregnation of active carbon (N/m) preoxidised with concentrated nitric acid at different temperatures. The amount of oxygen-containing surface groups on the supports was determined by infrared spectroscopy and X-ray photoelectron spectroscopy (XPS) while the distribution of active material was investigated using XPS. Catalytic activity of Fe³⁺-active carbon systems depended on the degree of the oxidation of the supports and pretreatment of the catalysts (drying, calcination in helium). The presence of oxygen in the reaction mixture enhanced the nitric oxide conversion. The catalysts showed a long-term stability.     

Characterization and catalytic properties of perovskites with nominal compositions La1-xSrxAl1-2yCuyRuyO3

Nine different metal oxide catalysts were prepared by impregnating alumina washcoats with water solutions containing La³⁺, Sr²⁺, Cu²⁺ and Ru³⁺ ions and calcining them at 900°C. The produced samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM) studies combined with energy-dispersive spectroscopy (EDS) analysis, X-ray powder diffraction and specific surface area measurements. A perovskite phase of the nominal composition La_1-xSr_xAl_1-2yCu_yRu_yO₃ was found in all samples, in increasing amount in the samples with increasing contents of strontium and ruthenium. The catalysts were evaluated with respect to light-off temperatures and redox characteristics using two gas mixtures, one containing NO/CO/C₃H₆/O₂/N₂ and the other NO/CO/N₂. The light-off temperatures for nitric oxide reduction decreased from 534 to 333°C for the catalysts without and with strontium and ruthenium, respectively. In the presence of oxygen the conversion of nitric oxide declined rapidly under oxidative conditions whereas in absence of oxygen this decline was less pronounced and found to be linear over the entire redox interval studied. These studies suggest that the perovskite phase takes an active part in the conversion of nitric oxide and carbon monoxide to nitrogen and carbon dioxide.     

Study of the NOχ reaction with reducing gases on Fe/ZrO2 catalyst

The Fe/ZrO₂ catalyst (1% Fe by weight) shows a strong adsorption capacity toward the nitric oxide (at room temperature the ratio NOFe is ca. 0.5) as a consequence of the formation of a highly dispersed iron phase after reduction at 500–773 K. Nitric oxide is adsorbed mainly as nitrosyl species on the reduced surface where the Fe²⁺ sites are prevailing, but it is easily oxidised by oxygen forming nitrito and nitrato species adsorbed on the support. However, in the presence of a reducing gas such as hydrogen, carbon monoxide, propane and ammonia at 473–573 K the Fe-nitrosyl species react producing nitrogen, nitrous oxide, carbon dioxide and water, as detected by FTIR and mass spectrometers. The results show that nitric oxide reduction is more facile with hydrogen containing molecules than with CO, probably due the co-operation of spillover effects. Experiments carried out with the same gases in the presence of oxygen show, however, a reduced dissociative activity of the surface iron sites toward the species NO_χ formed by NO oxidation and therefore the reactivity is shifted to higher temperatures.     

Alumina supported manganese oxides for the low-temperature selective catalytic reduction of nitric oxide with ammonia

Alumina supported manganese oxides exhibit a high and selective activity for the catalytic reduction of nitric oxide with ammonia (SCR) between 385 and 575 K. Samples with 3–15 wt.-% manganese were studied at space velocities between 22 000–116 000 h⁻¹ and at standard conditions of 500 ppm NO, 550 ppm NH₃ and 2% O₂. Manganese acetate results in a better dispersion of the manganese oxide on the support and a higher specific catalyst activity than manganese nitrate as precursor, for which crystalline structures could be detected. Temperature-programmed reduction revealed that acetate yields Mn₂O₃ and nitrate mainly MnO₂ on the γ-alumina support. The nitric oxide conversion per amount of manganese is fairly independent of the loading for the catalysts prepared from each precursor. The use of ¹⁵NH₃ reveals that it reacts in a 1:1 molar ratio with nitric oxide towards ¹⁵NN and/or ¹⁵NNO. The SCR activity (to nitrogen) is strongly dependent on the oxygen partial pressure, whereas water inhibits reversibly. Lattice oxygen of the catalyst is not able to maintain the SCR reaction in the absence of oxygen. The nitrous oxide formation is independent of the oxygen partial pressure, but increases with increasing manganese loading and with temperature, resulting in lower selectivities for nitrogen formation. The nitrogen and nitrous oxide formation probably occur at different sites. Above 525 K ¹⁵NH₃ oxidation occurs, yielding mainly ¹⁵N₂O and ¹⁵NO, depending on the temperature. The nitrous oxide is not further reduced by ammonia over this type of catalyst. The addition of tungsten to the catalyst increases the selectivity for nitrogen considerably. The stability of the ex-acetate catalyst is good, for at least 600 h the activity remained constant. The catalysts are sensitive towards sulphur dioxide, the ex-acetate catalysts the least, due to the strong interaction with the alumina support, as is revealed by TPR.     

Thermal stability of metal-supported catalysts for reduction of cold-start emissions in a wood-fired domestic boiler

The aim of the present work is to develop a catalyst based on a mixture of manganese oxides and platinum supported on a metallic monolith for abatement of emissions from wood combustion, particularly during the cold-start phase. The activity and the thermal stability of the catalysts have been studied in the laboratory, before performing tests in a wood-stove. The effect of the hydrothermal treatment at 900°C on the adherence of the washcoat onto a metallic substrate was studied using scanning electronic microscope. It revealed well-adhering washcoat onto the metallic support due to the growth of the alumina whiskers during the treatment. The influence of the amount of washcoat, as well as the influence of the concentration of manganese oxides in it (Mn: 5 to 20 mol%/Al₂O₃) on the activity of fresh and hydrothermally-treated catalysts were studied. The activity tests were carried out using a mixture of carbon monoxide, naphthalene and methane in the presence of air, steam and carbon dioxide to resemble the flue gases from wood combustion. On the fresh catalysts, containing the same total amount of manganese, a high concentration of manganese oxides in the washcoat favoured the oxidation of carbon monoxide and naphthalene, whereas a lower concentration of manganese oxides in the washcoat gave higher activity for the oxidation of methane. An increased total amount of manganese oxides in the catalysts, which had the same amount of washcoat, resulted in an increase in activity for the oxidation of the three combustibles. After thermal treatment at 900°C for 270 h in steam, most of the manganese oxide catalysts were activated for the oxidation of carbon monoxide and naphthalene while only being slightly deactivated for the oxidation of methane. The addition of manganese oxides in the washcoat, however, lowers the temperature of the γ- to -alumina phase transformation. Platinum (0.5 mol%) was added to the manganese oxide (10 mol%) catalyst to improve its activity. A platinum catalyst was also tested for comparison. The platinum and the mixed catalysts showed similar activity for the oxidation of carbon monoxide and naphthalene, while the mixed catalysts were more active for the oxidation of methane. A similarly mixed MnO_x–Pt (10–0.5 mol%) catalyst supported on Al₂O₃ stabilised with 3% lanthanum, but at larger scale, was tested in a wood-stove. The possibility of pre-heating the catalyst during the start-up phase was studied. The tests revealed a strong decrease of the carbon monoxide and unburned hydrocarbons emissions during the start-up phase when the catalyst was pre-heated with hot air compared with no pre-heating or no catalyst.     

EXPERIMENTAL STUDY OF CHARACTERISTICS OF Pt/TiO2 CATALYST

Chemisorption of hydrogen, carbon monoxide, and oxygen on 2 wt% Pt/TiO₂ was investigated to determine a satisfactory method for measuring the platinum dispersion on titania. The reduction of Pt/TiO₂ at high temperature results in sharp decrease in hydrogen and carbon monoxide chemisorption capacities and catalytic activity which cannot be accounted for by metal sintering. Oxidation-reduction treatments restore the usual properties of the catalyst. The TPD spectrum of hydrogen on Pt/TiO₃ shifts to higher temperature upon reduction at high temperature and shifts again to its original position upon oxidation. Shift of TPD spectrum does not appear in other catalysts. Oxygen adsorption method is inaccurate to measure crystallite diameter of platinum because oxygen uptake is enhanced not only due to reduced nonstoichiometric oxide support but also to penetration of oxygen into bulk platinum. Hydrogen chemisorption method, however, is a satisfactory technique to measure the platinum dispersion only if the strong metal-support bonding has been destroyed completely. Sintering rate in oxygen is greater than that in hydrogen regardless of the nature of the supports, and sintering resistance of Pt/TiO₂ in hydrogen is much greater than that of other supported platinum catalysts whereas stability of the platinum in oxygen is not dependent on the supports. The influence of chlorine in the presence of oxygen on the redispersion phenomena is found to be very important.     

CuO-ZnO-ZrO_2催化剂的还原性能及其低温CO催化氧化性能

采用共沉淀法制备得到CuO-ZnO-ZrO2催化剂及对比样品CuO-ZnO,通过XRD、BET、XPS、H2-TIR、H2-TPR等表征,考察了ZrO2的添加对CuO-ZnO-ZrO2催化剂的还原性能及其CO催化氧化性能的影响。与CuO-ZnO相比较,CuO-ZnO-ZrO2催化剂的比表面积增大、CuO和ZnO粒子的平均粒径减小、表面Cu粒子含量增多、还原性能得到显著提高,表明ZrO2的添加有利于提高CuO分散度,存在更多与ZnO相互作用的CuO微粒。TPR的还原动力学研究进一步证实了ZrO2对CuO还原性能的促进作用。在CO催化氧化反应中,CuO-ZnO-ZrO2样品的催化活性最高,并且还原温度对该催化剂的CO催化氧化性能影响显著,在160℃还原活化的催化剂具有77.3%的还原度,表现出较优的CO催化氧化性能。在50℃、3 MPa的反应条件下,CuO-ZnO-ZrO2催化剂可将液相丙烯中体积分数1.0×10-5的CO脱除低至2×10-8,连续反应1 500 min,稳定性能良好。     

Catalytic removal of SO2, NO and HCl from incineration flue gas over activated carbon-supported metal oxides

Activated carbon-supported copper, iron, or vanadium oxide catalysts were exposed to incineration flue gas to investigate the simultaneous catalytic oxidation of sulfur dioxide/hydrogen chloride and selective catalytic reduction of nitrogen oxide by carbon monoxide. The results show that AC-supported catalysts exhibit higher activities for SO₂ and HCl oxidation than traditional γ-Al₂O₃-supported catalysts and the iron and vanadium catalysts act as catalysts instead of sorbents, and can decompose sulfate with evolution of SO₃ and then regenerate for more SO₂ adsorption to take place. The AC-supported catalysts also display a high activity for NO reduction with CO generated from a flue gas incineration process and the presence of SO₂ in the incineration flue gas can significantly promote catalytic activity. Using CO as the reducing agent for NO reduction is more effective than using NH₃, because NH₃ may be partially oxidized in the presence of excess O₂ (12 vol%. in the incineration flue gas used) to form N₂, which can decrease the overall extent of NO reduction.     

Alternating nitrous oxide/reductant cycles and the determination of copper area in supported copper catalysts

Reduction, surface oxidation and re-reduction of a copper-on-silica catalyst has been investigated using hydrogen, carbon monoxide and nitrous oxide in a flow system with mass spectrometric determination. Hydrogen is more effective than carbon monoxide for the initial reduction of the catalyst as prepared in oxide form and the copper content can be accurately determined from the total gas consumption in both cases. However, carbon monoxide can quantitatively remove surface oxygen, deposited from nitrous oxide, at a temperature of 333 K, whereas the same process in hydrogen peaks at 383 K. A method for determining the quantity of surface copper by sequential N₂O/CO cycles under isothermal conditions has been established.     

Catalysts for Direct Methanol Fuel Cells

The activity of in house prepared carbon-supported Pt-Ru catalysts for methanol oxidation and carbon-supported RuSe for the oxygen reduction reaction in direct methanol fuel cells (DMFCs) was investigated. The composition of Pt-Ru/C was varied both in terms of weight loading (ratio of total metal content to carbon) as well as the ratio of Pt to Ru. The measurements were carried out in a half cell arrangement in sulphuric acid at various temperatures. The weight loading and ratio of Pt to Ru were varied in order to find out the optimum weight loading of precious metal and the temperature dependence of Pt to Ru ratio on methanol oxidation reaction. It has been found that there exists an optimum in the weight loading at 60 wt.% for carbon-supported Pt-Ru catalyst towards its maximum mass activity. While 1:1 Pt to Ru ratio exhibits a higher activity than 3:2 Pt:Ru above 60 °C, 3:2 ratio exhibits a higher activity at lower temperature. It has been observed that RuSe is inactive towards methanol and it is realised that RuSe is a potential candidate as methanol tolerant oxygen reduction catalyst. The activity of carbon supported RuSe for oxygen reduction reaction (ORR) was tested in sulphuric acid in the presence of methanol. Even though the mass specific activity of the RuSe catalyst is somewhat lower than that of Pt/C, the surface activity of carbon-supported RuSe is superior than that of carbon supported Pt which indicate the unfavourable size distribution of RuSe/C catalyst.     

Catalytic Properties of Ceria and CeO2-Containing Materials

Over the past several years, cerium oxide and CeO₂-containing materials have come under intense scrutiny as catalysts and as structural and electronic promoters of heterogeneous catalytic reactions. Recent developments regarding the characterization of ceria and CeO₂-containing catalysts are critically reviewed with a special focus towards catalyst interaction with small molecules such as hydrogen, carbon monoxide, oxygen, and nitric oxide. Relevant catalytic and technological applications such as the use of ceria in automotive exhaust emission control and in the formulation of SO _x reduction catalysts is described. A survey of the use of CeO₂-containing materials as oxidation and reduction catalysts is also presented.     

Study of the NOχ reaction with reducing gases on Fe/ZrO2 catalyst

The Fe/ZrO₂ catalyst (1% Fe by weight) shows a strong adsorption capacity toward the nitric oxide (at room temperature the ratio NOFe is ca. 0.5) as a consequence of the formation of a highly dispersed iron phase after reduction at 500–773 K. Nitric oxide is adsorbed mainly as nitrosyl species on the reduced surface where the Fe²⁺ sites are prevailing, but it is easily oxidised by oxygen forming nitrito and nitrato species adsorbed on the support. However, in the presence of a reducing gas such as hydrogen, carbon monoxide, propane and ammonia at 473–573 K the Fe-nitrosyl species react producing nitrogen, nitrous oxide, carbon dioxide and water, as detected by FTIR and mass spectrometers. The results show that nitric oxide reduction is more facile with hydrogen containing molecules than with CO, probably due the co-operation of spillover effects. Experiments carried out with the same gases in the presence of oxygen show, however, a reduced dissociative activity of the surface iron sites toward the species NO_χ formed by NO oxidation and therefore the reactivity is shifted to higher temperatures.     

Mechanism of low-temperature CO oxidation on a model Pd/Fe2O3 catalyst

A model Pd/Fe₂O₃ catalyst prepared by the vacuum technique has been studied in the carbon monoxide oxidation in the temperature range of 300–550 K at reagent pressures P(CO)=16 Torr, P(O₂)= 4 Torr. It has been shown that the activity of the fresh catalysts is determined by palladium. According to the XPS data, the reduction with carbon monoxide results in the formation of Fe²⁺ (formally Fe₃O₄) and appearance of the catalytic activity in this reaction at low temperatures (350 K). High low-temperature activity of the catalyst is supposed to be connected with the reaction between oxygen adsorbed on the reduced sites of the support (Fe²⁺) and CO adsorbed on palladium (CO_ads) at the metal–oxide interface.     

An investigation on the reaction mechanism for the partial oxidation of methane to synthesis gas over platinum

The partial oxidation of methane to synthesis gas has been investigated by admitting pulses of pure methane, pure oxygen and mixtures of methane and oxygen to platinum sponge at temperatures ranging from 973 to 1073 K. On reduced platinum the decomposition of methane results in the formation of surface carbon and hydrogen. No deposition of carbon occurs during the interaction of methane with a partly oxidised catalyst. Oxygen is present in three different forms under the conditions studied: platinum oxide, dissolved oxygen and chemisorbed oxygen species. Carbon monoxide and hydrogen are produced directly from methane via oxygen present as platinum oxide. Activation of methane involving dissolved oxygen provides a parallel route to carbon dioxide and water. Both platinum oxide and chemisorbed oxygen species are involved in the oxidation of carbon monoxide and hydrogen. In the presence of both methane and dioxygen at a stoichiometric feed ratio the dominant pathways are the direct formation of CO and H₂ followed by their consecutive oxidation. A Mars-van Krevelen redox cycle is postulated for the partial oxidation of methane: the oxidation of methane is accompanied by the reduction of platinum oxide, which is reoxidised by incorporation of dioxygen into the catalyst.     

汽车尾气净化催化剂的研制及其性能的研究

研究了 Cu- Co- Ce- Mn- Pd- K- O/γ- Al2 O3 催化剂的活性、热稳定性等。结果表明 ,该催化剂具有低温活性高 ,热稳定性好等特点。对 CO、C6H14 氧化的 t50 % 和 t98% 分别为 1 40°C、2 60°C和 1 80°C、2 95°C。催化剂活性组分间及它们与载体间存在着协同效应。Ce O2 的引入使各活性组分以高度分散的非结晶形态存在 ,这些是催化剂低的起燃温度、高活性的主要原因。另外 ,Ce O2 和 K2 O的引入赋予催化剂 90 0°C高温不烧结的良好热稳定性     

Influence of NH3 and NO oxidation on the SCR reaction mechanism on copper/nickel and vanadium oxide catalysts supported on alumina and titania

The influence of ammonia and nitric oxide oxidation on the selective catalytic reduction (SCR) of NO by ammonia with copper/nickel and vanadium oxide catalysts, supported on titania or alumina have been investigated, paying special attention to N₂O formation. In the SCR reaction, the VTi catalyst had a higher activity than VAl at low temperatures, while the CuNiAl catalyst had a higher activity than CuNiTi. A linear relationship between the reaction rate of ammonia oxidation and the initial reduction temperature of the catalysts obtained by H₂-TPR showed that the formation rate of NH species in copper/nickel catalysts would be higher than in vanadia catalysts. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) showed that copper/nickel catalysts presented ammonia coordinated on Lewis acid sites, whereas ammonium ion adsorbed on Brønsted acid sites dominated on vanadia catalysts. The NO oxidation experiments revealed that copper/nickel catalysts had an increase of the NO₂ and N₂O concentrations with the temperature. NO could be adsorbed on copper/nickel catalysts and the NO₂ intermediate species could play an important role in the reaction mechanism. It was suggested that the presence of adsorbed NO₂ species could be related to the N₂O formation.     

Nitric Oxide Catalysis in Automotive Exhaust Systems

This review covers the literature through 1991 on nitric oxide catalysis as applied to automobile exhaust systems. Attention is given to the threeway catalyst system which simultaneously promotes the reduction of nitrogen oxides and the oxidation of carbon monoxide and hydrocarbons. These systems have been used on most passenger cars in the United States since 1982. Prior to 1980, emission control catalysts were oxidation catalysts, and reduction in exhaust nitric oxide was achieved using engine modifications (i.e., exhaust gas recirculation). This review focuses on catalytic control of NO, for gasoline-fueled vehicles (not diesels and alternate fuels) and primarily on developments reported since 1982. The term NO, refers to both NO and NOz. The reader is referred to an earlier publication by the author for a general review of automobile catalytic converters [1] and to a review by Egelhoff [2] on the nitric oxide literature through 1980. The recent literature on NO, reduction in lean exhaust is cited although such catalyst systems have not reached commercial application.     

氧化处理对碳纳米纤维及其负载钯催化剂性能的影响

采用混合的浓硝酸和浓硫酸处理石墨层排布为鱼骨类和平行类的碳纳米纤维,分别用X-射线衍射、电子显微镜和N2-物理吸附研究了氧化处理对碳纳米纤维石墨层结构和织构性质的影响;利用FT—IR、酸碱滴定和热重分析对碳纳米纤维表面引入的舍氧基团进行了研究。结果表明,经过氧化处理的碳纳米纤维仍然保持类石墨结构。但织构性质在激烈的氧化条件下发生显著的改变。氧化处理在碳纳米纤维表面引入了大量的羧基基团,并且随着氧化处理温度的升高表面引入的羧基基团密度增大。在相同的氧化条件下,鱼骨类碳纤维表面生成的羧基基团的量明显高于平行类碳纳米纤维。以氧气为氧化剂,在没有溶剂的情况下,碳纳米纤维负载的Pd催化剂在基甲醇氧化反应中具有很高的活性,并且碳纳米纤维表面的羧基基团对其负载的Pd催化剂活性有明显的促进作用。