Towards the comprehension of oxygen storage processes on model three-way catalysts

CeO₂- and Ce_0.63Zr_0.37O₂-supported noble metal catalysts were studied. Samples were fully characterized using TEM, XRD, N₂ adsorption and H₂ chemisorption. The oxygen storage process was investigated focusing on the evolution as a function of temperature of both the oxygen storage capacity (OSC) and the oxygen storage complete capacity (OSCC). Aging effect on OSC was also examined in details in the case of Rh catalysts. Finally, the major role of oxygen diffusion, partly influenced by the metal/support interface quality, was confirmed.     

三效催化剂用储氧材料的研究进展

论述了国内外储氧材料的研究进展,简述了不同种类的储氧材料。对固溶体储氧材料CeO2的改性研究表明,过渡金属元素或稀土金属元素被嵌入CeO2晶格形成固溶体,可极大地改善CeO2基储氧材料的储氧性能和热稳定性能,促进CeO2基储氧材料广泛的实际应用。     

Reactivation of severely aged commercial three-way catalysts by washing with weak EDTA and oxalic acid solutions

Ethylene diamine tetraacetic acid (EDTA) which is a well-known reagent for its metal extraction efficiency was studied for the first time towards the improvement of the catalytic activity and oxygen storage and release properties (OSC) of severely aged commercial three-way catalysts (TWC) on a laboratory scale. Optimization of the experimental parameters of EDTA-washing procedure of TWC was carried out by varying the washing time, volumetric flow rate, and temperature of EDTA solution. The EDTA-washing procedure of TWC was compared with that of oxalic acid-washing regarding their efficiency in removing P, Pb, S, Ca, Zn, Fe, Cu, Cr, Ni, and Mn, all known TWC contaminants that many of them cause severe deterioration of TWC's activity and oxygen storage and release properties. EDTA appears to be significantly efficient in removing Pb, Zn, Ca, Mn, Fe, Cu and Ni metal contaminants and sulfur but not of phosphorus (P). Phosphorus-containing species were found to be efficiently removed from the aged TWCs after oxalic acid washing. All regeneration procedures applied led to a significant partial recovery of catalytic activity of TWC (CO, C_xH_y and NO_x conversions) under real exhaust gas conditions (dynamometer tests) due to the removal of large amounts of contaminants accumulated on the aged TWC. The washing procedures using oxalic acid alone or in combination with EDTA led to more significant improvements of both catalytic and OSC performance compared with those of EDTA washing alone. This was due to the ability of oxalic acid to remove P-containing compounds which appear to be one of the main causes of commercial three-way catalyst deactivation.     

Insights into the dynamics of oxygen storage/release phenomena in model ceria–zirconia catalysts as inferred from transient studies using H2, CO and soot as reductants

Samples of ceria–zirconia pre-treated under various conditions have been used as catalysts in CO and soot oxidation under stationary and transient conditions, in the presence and in the absence of oxygen. Their behaviour has been compared with that observed under redox conditions in the presence of hydrogen (oxygen storage activity). All the catalysts are active in CO and soot oxidation. Under stationary conditions, the activity in CO oxidation depends on the amount of Ce present, with little contribution from the redox capacity of the support and is strongly influenced by surface area. When the reaction is carried out under transient conditions, especially with low-surface area samples, the performances of ceria–zirconia are higher than those of ceria, with a maximum in the middle composition range. Interestingly, a similar behaviour is observed in soot combustion, where the activity for low-surface area sample is dependent on composition. This suggests that oxygen from the support plays a key role also in the oxidation of large carbon particles under a fully oxidizing mixture.     

Effects of catalyst aging on the activity and selectivity of commercial three-way catalysts

A Pd catalyst is particularly effective for the oxidation of CO and C₃H₆ at low temperatures, while the Pt/Rh/Ce catalyst is active for NO reduction. The TWC activity of both catalysts generally decreased as the catalyst mileage increased. However, the NO reduction activity was less affected by catalyst aging compared to the oxidation reactions. The selectivity of the catalysts in favor of the CO–O₂ reaction (vs. C₃H₆–O₂ reaction) in the O₂ partitioning experiments became less pronounced as the catalyst aged. The NO partitioning experiments reveal the superior capability of H₂ in NO reduction to the other reductants (CO and C₃H₆) examined in the present study. The reactivities of NO with both H₂ and CO were found to decrease upon catalyst aging, resulting in decreased overall NO removal activity.     

Effect of SO2 on the oxygen storage capacity of ceria-based catalysts

We have examined the effect of SO₂ poisoning on a series of catalysts having Pd supported on ceria, alumina, and ceria–zirconia. For pre-exposure of 20 ppm SO₂ at 673 K, we observed no changes in the light-off curves for CO oxidation on Pd/alumina. This pre-exposure of SO₂ to Pd/ceria resulted in a significant upward shift in the light-off curve, so that the poisoned Pd/ceria catalyst exhibited similar rates to that of Pd/alumina. Similar upward shifts were observed for the water–gas-shift reaction upon exposure of Pd/ceria or Pd/ceria–zirconia samples to SO₂. However, pulse-reactor data with alternating CO and O₂ pulses showed that SO₂ poisoning actually increased the amount of oxygen that could be transferred to and from the catalyst over the entire temperature range that was examined. The implication of these results for understanding the effect of SO₂ poisoning and the measurement of OSC are discussed.     

Investigation on properties of a novel ceria-zirconia-praseodymia solid solution and its application in Pd-only three-way catalyst for gasoline engine emission control

Different contents of praseodymia were introduced to modify Ce_0.2Zr_0.8O₂ (CZ) and the supported Pd-only three-way catalysts before and after aging were also prepared. The influence of praseodymia doping on the structural/textural properties of CZ and the effect on the three-way catalytic activity were investigated. Structural and textural characterizations reveal that the addition of praseodymia results in the formation of Ce-Zr-Pr ternary solid solution (CZP) with higher specific surface area, better thermal stability and larger oxygen storage capacity (OSC) than that of CZ. It is more credible that Zr is replaced by Pr during the formation of CZP. The modified Pd-only three-way catalysts present relatively higher catalytic activity to the main target pollutants in gasoline engine exhaust and exhibit wider air/fuel operation window due to the improved properties of CZP.     

Investigation of the oxygen storage process on ceria- and ceria–zirconia-supported catalysts

A total of 10 noble metal (Rh, Pt, Pd, Ru and Ir) catalysts, either supported on CeO₂ or Ce_0.63Zr_0.37O₂, were prepared. Catalysts were fully characterized using XRD, N₂ adsorption at −196 °C, TEM and H₂ chemisorption. Oxygen storage processes were carefully investigated. The influence of temperature was checked and a key role of oxygen diffusion was further demonstrated. A review of the reactions involved in the CO transient oxidation reaction is finally proposed.     

Correlation between activity and oxygen storage capacity of ceria on Pd-only three-way catalysts

One way of enhancing the thermal stability and NO_x, THC and CO conversion of a catalyst is to improve the thermal stability and oxygen storage capacity (OSC) of the ceria. The appropriate mixing ratios of bulk and stabilized ceria are especially very important for designing Pd-only three-way catalysts. In this paper, we discuss the surface phenomena of stabilized and unstabilized (bulk) ceria, the OSC of catalysts, and the correlation between activity and OSC of Pd-only catalysts with mixing ratios of bulk ceria and stabilized ceria.     

Characterization of the dynamic oxygen migration over Pt/CeO2-ZrO2 catalysts by O/O isotopic exchange reaction

To characterize the oxygen mobility over metal supported catalysts on a dynamic and in situ base, ¹⁸O/¹⁶O isotopic exchange reaction combined with CO oxidation was designed and exemplified on three kinds of three way catalysts of Pt/CeO₂-ZrO₂ (CZ-O, CZ-D and CZ-R). The obtained oxygen diffusion coefficients, oxygen release rate, and oxygen storage capacity were discussed and correlated with XRD spectra and other physical parameters. It was found that the oxygen mobility and oxygen storage capacity were parallel to the structural homogeneity of Zr introduction into the CeO₂ frame work, and decreased as: CZ-R > CZ-D > CZ-O. These results indicated that this combined isotopic exchange technique could be used to quantify the surface and bulk oxygen mobility, the oxygen storage capacity and oxygen release rate over the metal supported catalysts, and could be employed as a meaningful probe into the nature of CeO₂-ZrO₂ oxygen storage material. The oxygen mobility is also another important indicator for the development of oxygen storage materials.     

The use of temperature-programmed and dynamic/transient methods in catalysis: characterization of ceria-based, model three-way catalysts

Temperature-programmed (TP) methods have been increasingly used in recent years for the characterization of catalytic materials under conditions similar to those encountered in commercial applications. A large variety of complementary TP techniques can be used with minimum variation of experimental conditions, thus allowing great characterization potential in a single apparatus. Modern analytical and numerical tools allow accurate analysis and modeling of TP profiles, to obtain kinetic and other reaction parameters. Here, we will briefly review the experimental TP methods used for the characterization of the reduction features and the dynamic behavior of oxygen-storage/redox components of auto exhaust catalysts, based mainly on CeO₂ and ceria-zirconia.     

Axial characterization of oxygen storage capacity in close-coupled lightoff and underfloor catalytic converters and impact of sulfur

The oxygen storage capacity of a 56,000 mile aged warmup and underfloor converter system was characterized as a function of axial location along the converters and compared with fresh samples having the same formulation. Measurements of oxygen storage were made using a titration technique and at conditions expected to be commonly encountered during OBD-II diagnosis of catalyst performance. Vehicle aging resulted in a dramatic loss of oxygen storage in the warmup converter presumably due to the severe thermal sintering, but the significant amount of phosphorus (P) and zinc (Zn) poison accumulation on this converter was found to impact oxygen storage minimally. This is in contrast to the measured impact of P and Zn deposition on warmed-up hydrocarbon conversion, which was found to be significant relative to the impact of thermal sintering. The underfloor converter was found to have retained nearly all of its original oxygen storage after vehicle aging, consistent with operation of this converter at moderate temperatures which do no result in severe thermal sintering of the noble metals and the ceria.

The impact of sulfur on the oxygen storage of both warmup and underfloor converter sections was dramatic. Sections in the forward part of the warmup converter and in the front brick of the underfloor converter had relatively modest oxygen storage capacity which was almost completely blocked as the sulfur concentration reached 75–150 ppm (equivalent in gasoline). Other sections such as the rear of the warmup converter and the rear monolith of the underfloor converter had more oxygen storage capacity, which was significantly decreased as the sulfur concentration reached 150 ppm equivalent in fuel, and was approached complete loss near 500 ppm sulfur equivalent in fuel.     

The role of oxygen and hydroxyl support species on the mechanism of H2 production in the steam reforming of phenol over metal oxide-supported-Rh and -Fe catalysts

The aim of this work was to probe for the first time the back-spillover of labile O and OH species during steam reforming of phenol towards H₂ production over Rh and Fe supported on MgO, Mg-Ce-O and Mg-Ce-Zr-O metal oxides. This was made possible through SSITKA and other transient isotopic experiments (use of D₂O and ¹⁸O₂). The size of the active pool of H-containing species (H and/or OH) present under reaction conditions as a function of reaction T and catalyst composition, and deuterium kinetic isotope effects were measured.     

Defective structure, oxygen mobility, oxygen storage capacity, and redox properties of RE-based (RE = Ce, Pr) solid solutions

Defective structures, surface textures, oxygen mobility, oxygen storage capacity (OSC), and redox properties of RE_0.6Zr_0.4O₂ and of RE_0.6Zr_0.4−xY_xO₂ (RE=Ce, Pr; x=0, 0.05) solid solutions have been investigated using X-ray diffraction (XRD), temperature-programmed desorption (TPD), temperature-programmed reduction (TPR), O₂−H₂ and O₂−CO titration, ¹⁸O/¹⁶O isotope exchange, CO pulsing reaction, and X-ray photoelectron spectroscopy (XPS) techniques. The effects of doping noble metal onto RE_0.6Zr_0.4−xY_xO₂ on oxygen mobility and surface oxygen activities have also been studied. Based on the experimental outcomes, we conclude that: (i) a Pr-based solid solution has better redox behavior than a Ce-based one; (ii) incorporation of yttrium ions in the lattices of CZ and PZ solid solutions could result in an enhancement in oxygen vacancy concentration, Ce⁴⁺/Ce³⁺ and Pr⁴⁺/Pr³⁺ redox properties, lattice oxygen mobility, and oxygen storage capacity; and (iii) doping the noble metal (Rh, Pt, and Pd) onto RE-based solid solution has positive effect on the properties concerned in this work.     

Effect of specific surface area on oxygen storage capacity (OSC) and methane steam reforming reactivity of CeO<Subscript>2</Subscript>

It was found from the work that the specific surface area of ceria presents an important role on the oxygen storage capacity (OSC), the reactivity toward methane steam reforming, and the resistance toward carbon formation of this material. After calcination at 900°C, ceria prepared by surfactant-assisted method (SF) was observed from the present work to have significantly higher surface area than those prepared by templating (TP) and precipitation (PP) methods; this material showed strong OSC with good reforming reactivity in terms of thermal stability and resistance toward carbon formation compared to others. In detail, the degree of OSC was measured by the number of hydrogen uptake from the temperature programmed reduction (TPR). It was found that the value of hydrogen uptake from the TPR-1 of ceria prepared by SF was 2084 mmol g⁻¹, whereas those of ceria prepared by TP and PP were 1724 and 781 mmol g⁻¹, respectively. In addition, it was also proven in the present work that the OSC of these materials are reversible, according to the temperature programmed oxidation (TPO) and the second time temperature programmed reduction (TPR-2) results. According to the reactivity toward methane steam reforming, after purging in 3 kPa methane and 9 kPa steam at 900°C for 8 h, the methane conversion at steady state of ceria prepared by SF was approximately 38% with very low amount of carbon formed on the surface (0.16 mmol g⁻¹), whereas those of ceria prepared by TP and PP were 22% (with the amount of carbon formation of 0.30 mmol g⁻¹) and 13% (with the amount of carbon formation of 0.33 mmol g⁻¹), respectively.     

Effects of Pd particle size on the rates of oxygen back-spillover and CO oxidation under dynamic oxygen storage and release measurements over Pd/CeO2 catalysts

A kinetic mathematical model has been applied to investigate for the first time the effects of Pd particle size on the rates of oxygen back-spillover and CO oxidation during Oxygen Storage Capacity (OSC) measurements under dynamic conditions over Pd/CeO₂ catalysts in the 500–700 °C range. The dependence of the intrinsic rate constant k₁ of the CO oxidation reaction on PdO, and that of k ₂ ^app of the oxygen back-spillover from ceria to Pd/PdO on the palladium particle size was estimated by performing curve-fitting of the experimental CO and CO₂ pulse transient responses obtained. Activation energies of 8.0, 9.5 and 21.1 kJ/mol were calculated for the Eley–Rideal step of CO oxidation for the 1.3, 1.8 and 16.4 nm Pd particles, respectively, supported on CeO₂. The transient rates of CO oxidation and oxygen back-spillover were found to decrease with increasing Pd particle size.     

CO oxidation activity of gold catalysts supported on various oxides and their improvement by inclusion of an iron component

A number of oxide-supported gold catalysts have been prepared by deposition–precipitation, with variation of the pH over a wide range, the optimum pH for high activity being 9 for TiO₂, 7.5 for Fe₂O₃, and 7 for SnO₂ and CeO₂. Whereas the activity shown by Au/TiO₂ and Au/Fe₂O₃ decreased linearly with time, Au/CeO₂ and Au/SnO₂ underwent an initial major deactivation. Addition of iron in the preparation lowered the rate of deactivation when TiO₂, SnO₂ and CeO₂ were used as supports, and imparted activity when as with Bi₂O₃ it was previously lacking. XPS revealed the existence of a broad multi-state iron-containing region, and TEM and STEM/EDX indicated that small gold particles (1.5–4 nm) were partly in contact with it. Improved stability is therefore due to gold particles being in contact with an iron phase such as FeO(OH); calcination removed the stabilisation.     

Ambient temperature CO oxidation using copper manganese oxide catalysts prepared by coprecipitation: effect of ageing on catalyst performance

Copper manganese oxides are prepared using a coprecipitation procedure and studied for the oxidation of CO at ambient temperature. In particular, the effect of the ageing tune, i.e. the time that the precipitate remains in contact with the precipitating medium, is investigated. It is shown that this parameter is of crucial importance in controlling the catalytic performance and that catalysts which are aged for 30 min or 300 min give the best performance. Preliminary characterisation using powder X-ray diffraction indicates that a combination between CuO and copper manganese oxide may be responsible for the enhanced activity observed with these samples.     

All-in-one functional supramolecular nanoparticles based on pillar[5]arene for controlled generation,storage and release of singlet oxygen

The storage and controlled release of singlet oxygen (¹O₂) have attracted increasing attention due to the wide application and microsecond lifetime of ¹O₂ in water. Herein we provide an integrated nanoplatform consisting of a diphenylanthracene derivative, a water-soluble pillar[5]arene and a photosensitizer tetrakis(4-hydroxyphenyl)porphyrin (TPP), that may provide the controlled generation, storage and release of singlet oxygen. We design a new diphenylanthracene derivative with two trimethylammonium bromide groups on both ends that can be well recognized by the pillar[5]arene. The formed nanocarriers can be used to load TPP through their supramolecular self-assembly. The resulting nanoparticles show good water-solubility and uniform spherical morphology. After laser irradiation (660 nm), the nanoparticles exhibit excellent ability for the generation and storage of ¹O₂. When the irradiated nanoparticles are heated above 80 °C, ¹O₂ can be released from the system. Therefore, in this paper we pioneer the use of noncovalent interaction to integrate the diphenylanthracene derivatives and photosensitizers into one functional system, which provides a new strategy for the controlled generation, storage and release of singlet oxygen. We believe this groundbreaking strategy will have a great potential in providing necessary amounts of ¹O₂ for the photodynamic therapy of tumors in dark.