Potential rare-earth modified CeO2 catalysts for soot oxidation part II: Characterisation and catalytic activity with NO + O2

Ceria (CeO₂) and rare-earth modified ceria (CeReO_x with Re = La³⁺, Pr^3+/4+, Sm³⁺, Y³⁺) supports and Pt impregnated supports are studied for the soot oxidation under a loose contact with the catalyst with the feed gas, containing NO + O₂. The catalysts are characterised by XRD, H₂-TPR, DRIFT and Raman spectroscopy. Among the single component oxides, CeO₂ is significantly more active compared with the other lanthanide oxides used in this study. Doping CeO₂ with Pr^3+/4+ and La³⁺ improved, however, the soot oxidation activity of the resulting solid solutions. This improvement is correlated with the surface area in the case of CeLaO_x and to the surface area and redox properties of CePrO_x catalyst. The NO conversion to NO₂ over these catalysts is responsible for the soot oxidation activity. If the activity per unit surface area is compared CePrO_x is the most active one. This indicates that though La³⁺ can stabilise the surface area of the catalyst in fact it decreases the soot oxidation activity of Ce⁴⁺. The lattice oxygen participates in NO conversion to NO₂ and the rate of this lattice oxygen transfer is much faster on CePrO_x. In general, the improvement of the soot oxidation is observed over the Pt impregnated CeO₂ and CeReO_x catalysts, and can be correlated to the presence of Pt°. The surface reduction of the supports in the presence of Pt occurred below 100 °C. The surface redox properties of the support in the Pt catalysts do not have a significant role in the NO to NO₂ conversion. In spite of the lower surface area, the Pt/CeYO_x and Pt/CeO₂ catalysts are found to be more active due to larger Pt crystal sizes. The presence of Pt also improved the CO conversion to CO₂ over these catalysts. The activation energy for the soot oxidation with NO + O₂ is found to be around 50 kJ/mol.     

Potential rare earth modified CeO2 catalysts for soot oxidation: I. Characterisation and catalytic activity with O2

Ceria (CeO₂) and rare-earth modified ceria (CeReO_x with Re = La, Pr, Sm, Y) catalysts are prepared by nitrate precursor calcination and are characterised by BET surface area, XRD, H₂-TPR, and Raman spectroscopy. Potential of the catalysts in the soot oxidation is evaluated in TGA with a feed gas containing O₂. Seven hundred degree Celsius calcination leads to a decrease in the surface area of the rare-earth modified CeO₂ compared with CeO₂. However, an increase in the meso/macro pore volume, an important parameter for the soot oxidation with O₂, is observed. Rare-earth ion doping led to the stabilisation of the CeO₂ surface area when calcined at 1000 °C. XRD, H₂-TPR, and Raman characterisation show a solid solution formation in most of the mixed oxide catalysts. Surface segregation of dopant and even separate phases, in CeSmO_x and CeYO_x catalysts, are, however, observed. CePrO_x and CeLaO_x catalysts show superior soot oxidation activity (100% soot oxidation below 550 °C) compared with CeSmO_x, CeYO_x, and CeO₂. The improved soot oxidation activity of rare-earth doped CeO₂ catalysts with O₂ can be correlated with the increased meso/micro pore volume and stabilisation of external surface area. The segregation of the phases and the enrichment of the catalyst surface with unreducible dopant decrease the intrinsic soot oxidation activity of the potential CeO₂ catalytic sites. Doping CeO₂ with a reducible ion such as Pr^4+/3+ shows an increase in the soot oxidation. However, the ease of catalyst reduction and the bulk oxygen-storage capacity is not a critical parameter in the determination of the soot oxidation activity. During the soot oxidation with O₂, the function of the catalyst is to increase the ‘active oxygen’ transfer to the soot surface, but it does not change the rate-determining step, as evident from the unchanged apparent activation energy (around 150 kJ mol⁻¹), for the catalysed and un-catalysed soot oxidation. Spill over of oxygen on the soot surface and its subsequent adsorption at the active carbon sites is an important intermediate step in the soot oxidation mechanism.     

Potential rare-earth modified CeO2 catalysts for soot oxidation

The physico-chemical properties of ceria (CeO₂) and rare earth modified ceria (with La, Pr, Sm, Y) catalysts are studied and correlated with the soot oxidation activity with using O₂ and O₂ + NO. CeO₂ modified with La and Pr shows superior soot oxidation activity with O₂ compared with the unmodified catalyst. The improved soot oxidation activity of rare earth doped CeO₂ catalysts can be correlated to the increased meso/micro pore volume and the stabilisation of the external surface area. On the other hand, unreducible ions decrease the intrinsic soot oxidation activity of rare earth modified ceria with both O₂ and NO + O₂ due to the decreased amount of redox surface sites. The catalyst bulk oxygen storage capacity is not a critical parameter in determining the soot oxidation activity. The modification with Pr shows the best soot oxidation with both O₂ and O₂ + NO compared with all other catalysts.     

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.     

Co3O4–CeO2 mixed oxide-based catalytic materials for diesel soot oxidation

Co₃O₄–CeO₂ type mixed oxide catalyst compositions have been prepared by using co-precipitation method and, their catalytic activity towards diesel particulate matter (PM)/carbon oxidation has been evaluated under both loose and tight contact conditions. These catalysts show excellent catalytic activity for PM/carbon oxidation, despite their low surface area. The activation energy observed for non-catalyzed and catalyzed reactions are 163 kJ/mol and 140 kJ/mol, respectively, which also confirm the catalytic activity of catalyst for carbon/soot oxidation. The promotional effects of an optimum amount of cobalt oxide incorporation in ceria and presence of a small amount of potassium appears to be responsible for the excellent soot oxidation activity of this mixed oxide type material. The catalytic materials show good thermal stability, while their low cost will also add to their potential for practical applications.     

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.     

Comparison of catalytic activity and selectivity of Pd/(OSC + Al2O3) and (Pd + OSC)/Al2O3 catalysts

The effect of the Pd addition method into the fresh Pd/(OSC + Al₂O₃) and (Pd + OSC)/Al₂O₃ catalysts (OSC material = Ce_xZr_1−xO₂ mixed oxides) was investigated in this study. The CO + NO and CO + NO + O₂ model reactions were studied over fresh and aged catalysts. The differences in the fresh catalysts were insignificant compared to the aged catalysts. During the CO + NO reaction, only small differences were observed in the behaviour of the fresh catalysts. The light-off temperature of CO was about 20 °C lower for the fresh Pd/(OSC + Al₂O₃) catalyst than for the fresh (Pd + OSC)/Al₂O₃ catalyst during the CO + NO + O₂ reaction. For the aged catalysts lower NO reduction and CO oxidation activities were observed, as expected. Pd on OSC-containing alumina was more active than Pd on OSC material after the agings. The activity decline is due to a decrease in the number of active sites on the surface, which was observed as a larger Pd particle size for aged catalysts than for fresh catalysts. In addition, the oxygen storage capacity of the aged Pd/(OSC + Al₂O₃) catalyst was higher than that of the (Pd + OSC)/Al₂O₃ catalyst.     

Effect of calcination temperature on the low-temperature oxidation of CO over CoOx/TiO2 catalysts

A 5 wt% CoO_x/TiO₂ catalyst has been used to study the effect of calcination temperature on the activity of this catalyst for CO oxidation at 100 °C under a net oxidizing condition in a continuous flow type fixed-bed reactor system, and the catalyst samples have been characterized using TPD, XPS and XRD measurements. The catalyst after calcination at 450 °C gave highest activity for this low-temperature CO oxidation, and XPS measurements yielded that a 780.2-eV Co 2p_3/2 main peak appeared with this catalyst sample and this binding energy was similar to that measured with pure Co₃O₄. After calcination at 570 °C, the catalyst, which had possessed practically no activity in the oxidation reaction, gave a Co 2p_3/2 main structure peak at 781.3 eV which was very similar to those obtained for synthesized Co_nTiO_n+2 compounds (CoTiO₃ and Co₂TiO₄), and this catalyst sample had relatively negligible CO chemisorption as observed by TPD spectra. XRD peaks indicating only the formation of Co₃O₄ particles on titania surface were developed in the catalyst samples after calcination at temperatures ≥350 °C. Based on these characterization results, five types of Co species could be modeled to exist with the catalyst calcined at different temperatures. Among these surface Co species, the Type A clean Co₃O₄ particles were predominant on a sample of the catalyst after calcination at 450 °C and highly active for CO oxidation at 100 °C, and the calcination at 570 °C gave the Type B Co₃O₄ particles with complete Co_nTiO_n+2 overlayers inactive for this oxidation reaction.     

Nd2O3基复合氧化物上炭黑和NOx的同时催化去除特性

利用程序升温反应（TPR）技术，对同时催化去除柴油机炭黑和氮氧化物反应进行了研究.结果表明：稀土金属氧化物及其负载金属氧化物能在富氧条件下使炭黑（C）和氮氧化物（NO_x）互为氧化还原，主要生成CO₂和N₂，达到C-NO_x两者的同时催化去除.在Nd₂O₃等稀土氧化物上负载K和Mn等金属氧化物能降低炭黑的起燃温度，提高NO的还原转化率，其中K/Mn/Nd₂O₃ 上的催化反应同无催化反应相比，其炭黑起燃温度降低了170℃，最大NO→N₂转化率达到75.4％.K能显著降低起燃温度，并存在最佳负载量（2 mmol•g^-1）.K负载量过多，可能导致稀土金属氧化物上原有活性位的覆没.     

Evaluation of carbon monoxide oxidation over CeO2/Co3O4 catalysts: Effect of ceria loading

Modification of cobaltic oxide (obtained from the reduction of high-valence cobalt oxide and assigned as R230, S_BET = 100 m² g⁻¹) with different loading of ceria was proceeded using the impregnation method (assigned as CeX/R230, X = 4, 12, 20, 35 and 50 wt%). The CeX/R230 catalysts were characterized by X-ray diffraction (XRD), nitrogen adsorption at −196 °C, temperature-programmed reduction (TPR) and transmission electron microscopy (TEM). Their catalytic activities towards the CO oxidation were studied in a continuous flow micro-reactor. The results revealed that the optimal modification, i.e., Ce20/R230, can increase the surface area (S_BET = 109 m² g⁻¹) of cobaltic oxide, further weaken the bond strength of CoO and lower the activation of CO oxidation among CeX/R230 catalysts due to the combined effect of cobaltic oxide and ceria. The Ce20/R230 catalyst exhibited the best catalytic activity in CO oxidation with T₅₀ (temperature for 50% CO conversion) at 88 °C.     

Catalytic wet oxidation of phenol over PtxAg1−xMnO2/CeO2 catalysts

Catalytic wet oxidation reactions of aqueous phenol over unpromoted, base- and noble-metal promoted MnO₂/CeO₂ catalysts were carried out under mild conditions (80–130°C, 0.5 MPa O₂) in a batch slurry reactor. Even though the catalyst-mediated oxidation was very effective in destroying phenol, only a moderate selectivity toward complete mineralization into CO₂ and H₂O was attained due to parallel formation of deactivating carbonaceous deposits. Promotion of the mixed-oxide catalysts with platinum and/or silver enhanced the mineralization selectivity and reduced appreciably the amount of deposits.     

Catalytic combustion of diesel soot particles on copper catalysts supported on TiO2. Effect of potassium promoter on the activity

We have prepared a TiO₂ supported copper catalyst and studied the effect of potassium on its activity in the oxidation of soot particles. The catalysts, with a K/Cu atomic ratio varying between 0 and 2, were calcined at 1073 K. They were characterized by BET surface area measurements, X-ray diffraction and temperature-programmed reduction under hydrogen. The catalytic activity was measured in a microbalance by means of temperature-programmed oxidation in air or argon. The catalytic activity of copper was enhanced by the presence of potassium. This effect was attributed to the formation of mixed K---Ti oxides which inhibit the sintering of the TiO₂ support and thus increases the surface area of the catalyst. Although a redox mechanism can explain the catalytic combustion, no correlation could be established between the reducibility of the different solids and their activity in soot combustion.     

Catalytic effect of platinum on the kinetics of carbon oxidation by NO2 and O2

The effect of a commercial Pt/Al₂O₃ catalyst on the oxidation by NO₂ and O₂ of a model soot (carbon black) in conditions close to automotive exhaust gas aftertreatment is investigated. Isothermal oxidations of a physical mixture of carbon black and catalyst in a fixed bed reactor were performed in the temperature range 300–450 °C. The experimental results indicate that no significant effect of the Pt catalyst on the direct oxidation of carbon by O₂ and NO₂ is observed. However, in presence of NO₂–O₂ mixture, it is found that besides the well established catalytic reoxidation of NO into NO₂, Pt also exerts a catalytic effect on the cooperative carbon–NO₂–O₂ oxidation reaction. An overall mechanism involving the formation of atomic oxygen over Pt sites followed by its transfer to the carbon surface is established. Thus, the presence of Pt catalyst increases the surface concentration of –C(O) complexes which then react with NO₂ leading to an enhanced carbon consumption. The resulting kinetic equation allows to model more precisely the catalytic regeneration of soot traps for automotive applications.     

Metal-loaded CeO2-ZrO2 solid solutions as innovative catalysts for automotive catalytic converters

The redox behaviour of a Ce_0.5Zr_0.5O₂ solid solution is investigated by means of temperature programmed reduction (TPR) and oxygen uptake measurements. It is shown that the introduction of ZrO₂ into the CeO₂ framework, strongly modifies the reduction behaviour in comparison to pure CeO₂. Remarkably, in contrast to the CeO₂, upon repetitive reduction-oxidation processes, the temperature of reduction of the solid solution decreases from 900 to 700 K. The reduction of NO by CO over metal-loaded catalysts is investigated and the role of support Ce³⁺ sites in the enhancing the NO conversion is discussed.     

Characterization and catalytic activity of Pd/V2O5/Al2O3 catalysts on benzene total oxidation

The role of vanadium oxide and palladium on the benzene oxidation reaction over Pd/V₂O₅/Al₂O₃ catalysts was investigated. The Pd/V₂O₅/Al₂O₃ catalysts were more active than V₂O₅/Al₂O₃ and Pd/Al₂O₃ catalysts. The increase of vanadium oxide content decreased the Pd dispersion and increased the benzene conversion. A strong Pd particle size effect on benzene oxidation reaction was observed. Although the catalysts containing high amount of V⁴⁺ species were more active, the Pd particle size effect was responsible for the higher activity.     

The effect of potassium on the Ir/C3H6 + NO + O2 catalytic system

The C₃H₆ + NO + O₂ reaction has been studied in a wide range of temperatures (ca. 250–400 °C) and oxygen concentrations (0–5% O₂) over potassium-modified Ir surfaces. The in situ electrochemical controlled concept of catalysts promotion was used by interfacing a polycrystalline Ir thin film with a potassium β″-Al₂O₃ solid electrolyte disc, a K⁺ conductor. At low oxygen concentrations (i.e., at reducing conditions), the effect of potassium on the Ir activity and selectivity is negligible. However, at higher oxygen concentrations (oxidizing conditions), strong K-induced poisoning on both propene and NO turnover consumption rates, as high as 85% and 65%, respectively, were recorded. Significant reduction on the system selectivity towards N₂ was also recorded under these conditions (from 100% over K-free Ir surface to 70% on K-modified Ir surfaces). The performance of Ir under alkali promotion is dramatically different to that reported in the literature for Pt or Pd under similar conditions, where strong promotional effects have been found. This very different behaviour may be understood in terms of the electronic influence of co-adsorbed potassium on the adsorption strengths of the neighbor reactants on the Ir surface.     

The catalytic activity of FeOx/ZrO2 for the abatement of NO with propene in the presence of O2

FeO_x/ZrO₂ samples, prepared by impregnation with Fe(NO₃)₃, were characterised by means of DRS, XRD, FTIR, redox cycles and volumetric CO adsorption. Volumetric CO adsorption, combined with FTIR, showed that 45% of iron in the sample containing 2.8 Fe atoms nm⁻² was capable of forming iron carbonyls. DRS evidenced Fe₂O₃ on samples with Fe-content≥2.8 atoms nm⁻². The selective catalytic reduction of NO with C₃H₆ in the presence of O₂ was studied with a reactant mixture containing NO=4000 ppm, C₃H₆=4000 ppm, O₂=2%. The dependence on iron-content suggests that only isolated iron, prevailing in dilute FeO_x/ZrO₂, is active for NO reduction, whereas iron on the surface of small oxide particles, prevailing in concentrated FeO_x/ZrO₂, is active for C₃H₆ combustion.     

CO oxidation catalysts based on copper and manganese or cobalt oxides supported on MgF2 and Al2O3

The catalytic activity of a mixed phase of copper–cobalt and copper–manganese oxides supported on magnesium fluorine or alumina has been studied in low temperature CO oxidation at 30 °C. During calcination, the oxides studied partially react to form different type spinels depending on the calcination temperature. These spinels have different effect on the catalytic activity. In low temperature CO oxidation the copper–manganese catalysts are more active than the copper–cobalt ones.     

过渡金属氧化物负载对Nd2O3基催化剂同时去除NOx-炭烟活性的影响

利用程序升温反应技术（TPR）详细考察了负载K和不同过渡金属在Nd₂O₃ 基复合氧化物催化剂的催化活性，探讨了不同负载量对NOx－炭烟同时催化去除活性的影响。研究结果表明，负载Cr具有最好的炭烟催化活性，其最佳负载质量分数为10%；负载Mn具有最大的NOx→N₂转化率；复合晶相的生成提高NOx－炭烟同时催化去除活性。     

An exploratory study of diesel soot oxidation with NO2 and O2 on supported metal oxide catalysts

A number of supported metal oxide catalysts were screened for their catalytic performance for the oxidation of carbon black (CB; a model diesel soot) using NO₂ as the main oxidant. It was found that contact between the carbon and catalyst was a key factor in determining the rate of oxidation by NO₂. Oxides with low melting points, such as Re₂O₇, MoO₃ and V₂O₅ showed higher activities than did Fe₃O₄ and Co₃O₄. The activities of MoO₃ and V₂O₅ on various supporting materials were also examined. MoO₃/SiO₂ was the most active catalyst among the supported MoO₃ examined, whereas, V₂O₅/MCM-41 showed the highest activity among the supported V₂O₅. Different performances of the supported MoO₃ catalysts were explained by the interaction of MoO₃ with the supports: a strong MoO₃/support interaction may result in a poor mobility of MoO₃ and a poor activity for oxidation of carbon by NO₂. The high activity of V₂O₅/MCM-41 was associated with its catalysis of the oxidation of SO₂ by NO₂ to form SO₃, which substantially promotes oxidation of carbon by NO₂. Addition of transition metal oxides or sulfates to supported MoO₃ and V₂O₅ was also investigated. Combining MoO₃ or V₂O₅ with CuO on SiO₂, adding VOSO₄ to MoO₃/SiO₂ or MoO₃/Al₂O₃ and adding TiOSO₄ or CuSO₄ to V₂O₅/Al₂O₃ improved the catalytic performance.