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.     

X-ray absorption fine structure analysis of local structure of CeO2–ZrO2 mixed oxides with the same composition ratio (Ce/Zr=1)

Three types of CeO₂–ZrO₂ (Ce:Zr=1:1 molar ratio) compounds with different oxygen storage/release capacities (OSCs) were characterized by means of the Ce K-edge and Zr K-edge X-ray absorption fine structure (XAFS). In order to investigate the relationship between the OSC and local structure, the quantitative EXAFS curve-fitting analysis was applied. By enhancing the homogeneity of the Ce and Zr atoms in the CeO₂–ZrO₂ solid solution, the OSC performance increased. Especially, the atomically homogeneous Ce_0.5Zr_0.5O₂ solid solution exhibited the highest OSC among these CeO₂–ZrO₂ samples. Additionally, the local oxygen environment around Ce and Zr was remarkably modified by enhancing the homogeneity of the CeO₂–ZrO₂ solid solution. It was postulated that the enhancement of the homogeneity of the CeO₂–ZrO₂ solid solution and the modification of the oxygen environment would be the source for the OSC improvement.     

Dynamics of oxygen storage and release on commercial aged Pd-Rh three-way catalysts and their characterization by transient experiments

The present work has provided new fundamental information on the effects of aging (mileage, km) of a commercial Pd-Rh (9:1, w/w) three-way catalyst (TWC) on (a) the H₂ chemisorption, (b) the redox properties of washcoat material, and (c) the dynamic oxygen storage and release properties of TWC. Hydrogen chemisorption in the 25–400 °C range was found to decrease with increasing aging of TWC. On the other hand, H₂ chemisorption performed at 200 and 400 °C resulted in a significantly larger amount of chemisorbed hydrogen (exceeding the monolayer value based on the noble metals) compared to that obtained after chemisorption at 25 °C. This is due to the onset of a hydrogen spill over process in the 200–400 °C range. The features of H₂-TPD spectra were found to strongly depend on the aging of TWC. Hydrogen chemisorption at 25 °C followed by TPD after a given pre-treatment of the catalyst surface might be considered as a procedure for a good estimate of the metal dispersion of a commercial Pd-Rh TWC. The redox properties of the oxygen storage components of the washcoat of a commercial Pd-Rh TWC were found to drastically change with increasing aging of TWC. It was found that the oxygen storage capacity (OSC) of the TWC investigated decreases significantly with catalyst aging in the 0–56,000 km range and in the temperature range of 500–750 °C. In the case of fresh TWC, the presence of 20 ppm SO₂ or 10% CO₂ in a 1.5% O₂/He gas mixture used for oxygen storage (oxidizing gas) was found to result in a large decrease in the amount of dynamic OSC measured by alternating switches between oxidizing and reducing feed gas compositions. The shift in time of the peak maximum of the transient response of CO₂ obtained during the switch O₂/He → He → CO/He (t) can be ascribed to the alteration of the kinetics of the oxygen back-spillover process and not to the kinetics of CO oxidation on the metal surface.     

A new concept in high performance ceria–zirconia oxygen storage capacity material with Al2O3 as a diffusion barrier

CeO₂–ZrO₂ solid solution ((Ce,Zr)O₂) is an indispensable oxygen storage capacity (OSC) material for emission control in gasoline-fuelled automobiles. The high performance OSC material developed in this study is composed of Al₂O₃ as “a diffusion barrier” and (Ce,Zr)O₂ particles in intervening layers on a nanometer scale, and is abbreviated as “ACZ”. The Brunauer–Emmett–Teller (BET) specific surface area (SSA) of ACZ after durability testing in air at 1000 °C was 20 m²/g, which is higher than that of conventional CZ (2 m²/g) composed of (Ce,Zr)O₂ without Al₂O₃. After heat treatment at 1000 °C in air, the particle size of (Ce,Zr)O₂ in ACZ was about 10 nm and that without Al₂O₃ was one-half of the size in pure CZ. The OSC was roughly characterized by the total capacity (OSC-c1) and the oxygen release rate (OSC-r). In a fresh catalyst, ACZ and CZ had almost the same OSC-c1; however, the OSC-r of ACZ was twice as fast as CZ. After durability testing, the OSC-r of both ACZ and CZ were reduced significantly, but the OSC-r of ACZ was about five times as fast as CZ. While the OSC-c1 was hardly influenced by the (Ce,Zr)O₂ crystallite size and Pt particle size on the supports, the OSC-r was influenced by both of these parameters. The improvement of the OSC-r in the fresh catalyst and inhibition of the decrease in the OSC-r after durability testing were achieved by suppression of particle growth of (Ce,Zr)O₂ in ACZ by introducing Al₂O₃ as a diffusion barrier with resultant inhibition of sintering of Pt particles.     

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.     

Modification of the oxygen storage capacity of CeO2–ZrO2 mixed oxides after redox cycling aging

High surface area CeO₂–ZrO₂ mixed oxides were treated at 900–950°C either under wet air or under successive reducing and oxidizing atmospheres in order to study the evolution of the oxygen storage capacity (OSC) of these solids after different aging treatments. Several complementary methods were used to characterize the redox behavior: temperature programmed reduction (TPR) by H₂, TPO, magnetic susceptibility measurements to obtain the Ce³⁺ content, FT-IR spectroscopy of adsorbed methanol and a method to compare the oxygen buffering capacity (OBC) of the oxides.

All the results confirm that the mixed oxides exhibit better redox properties than pure ceria, particularly after aging. The enhancement in the OSC at moderate temperature has to be related to a deeper penetration of the reduction process from the surface into the under-layers. Redox cycling aging promotes the reduction at low temperature of all the mixed oxides, the improvement being much more important for low surface area aged samples. The magnitude of this effect does not depend on the BET surface areas which have similar values after cycling. This underlines the critical influence that the preparation and activation procedure have on the final OSC behaviors of the ceria–zirconia mixed oxides.     

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.     

Thermal ageing of Pt on low-surface-area CeO2–ZrO2–La2O3 mixed oxides: Effect on the OSC performance

This work aims at exploring the thermal ageing mechanism of Pt on ceria-based mixed oxides and the corresponding effect on the oxygen storage capacity (OSC) performance of the support material. Pt was supported on low-surface-area CeO₂–ZrO₂–La₂O₃ mixed oxides (CK) by impregnation method and subsequently calcined in static air at 500, 700 and 900 °C, respectively. The evolutions of textural, microstructural and redox properties of catalysts after the thermal treatments were identified by means of X-ray diffraction (XRD), Raman, X-ray photoelectron spectroscopy (XPS), temperature programmed reduction (TPR) and high-resolution transmission electron microscope (HRTEM). The results reveal that, besides the sintering of Pt, encapsulation of metal by the mixed oxides occurs at the calcination temperature of 700 °C and above. The burial of Pt crystallites by support particles is proposed as a potential mechanism for the encapsulation. Further, the HRTEM images show that the distortion of the mixed oxides lattice and other crystal defects are distributed at the metal/oxides interface, probably indicating the interdiffusion/interaction between the metal and mixed oxide. In this way, encapsulation of Pt is capable to promote the formation of Ce³⁺ or oxygen vacancy on the surface and in the bulk of support. The OSC results show that the reducibility and oxygen release behavior of catalysts are related to both the metal dispersion and metal/oxides interface, and the latter seems to be more crucial for those supported on low-surface-area mixed oxides. Judging by the dynamic oxygen storage capacity (DOSC), oxygen storage capacity complete (OSCC) and oxygen releasing rate, the catalyst calcined at 700 °C shows the best OSC performance. This evident promotion of OSC performance is believed to benefit from the partial encapsulation of Pt species, which leads to the increment of Ce³⁺ or oxygen vacancies both on the surface and in the bulk of oxides despite a loss of chemisorption sites on the surface of metal particles.     

The effect of ceria content on the performance of Pt/CeO2/Al2O3 catalysts in the partial oxidation of methane

The effect of CeO₂ loading (1–20 wt.%) on the properties and catalytic behaviors of CeO₂–Al₂O₃-supported Pt catalysts on the partial oxidation of methane was studied. The catalysts were characterized by S_BET, X-ray diffraction (XRD), temperature-programmed reduction (TPR) and oxygen storage capacity (OSC). XRD and TPR results showed that the pretreatment temperature of the support influences on the amount of CeO₂ with fluorite structure. The pretreatment temperature of the support and CeO₂ loading influenced the morphology of Pt. OSC analysis showed a significant increase in the oxygen storage capacity per weight of CeO₂ for samples with high CeO₂ loading (12 and 20 wt.%). TPR analyses showed that the addition of Pt promotes the reduction of CeO₂. This effect was more significant for the catalysts with high CeO₂ loading (≥12 wt.%). The dispersion of Pt, measured by the rate of cyclohexane dehydrogenation, increases with increasing of the pretreatment temperature of the support. It was shown that the kind of the support is very important for obtaining of catalysts resistant to carbon formation. The catalysts with high CeO₂ loading (≥12 wt.%) showed the highest catalytic activity and stability in the reaction of partial oxidation of methane due to a higher Pt–CeO₂ interface.     

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.     

Nanophase catalytic oxides: I. Synthesis of doped cerium oxides as oxygen storage promoters

Doped CeO₂ materials were synthesized with the aim to improve the performance of CeO₂ as oxygen storage promoter in gas catalytic reactions. The coprecipitation method was used for the synthesis of fine oxalate precursors of high homogeneity and well defined composition. The chemical and morphological properties of both the coprecipitated oxalates and the calcined oxides were examined. The influence of doping of different metal cations into the CeO₂ structure on the oxygen storage capacity in particular was investigated. Some of the doped oxides Ce_0.9M_0.1 O_{2 − δ} (M = Ca, Nd, Pb, etc.) give an increased oxygen storage capacity, 20–40% higher than the undoped. Their redox activity also remarkably increased.     

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.     

Cerium–terbium mixed oxides as alternative components for three-way catalysts: a comparative study of Pt/CeTbOx and Pt/CeO2 model systems

By using a combination of oxygen buffering capacity (OBC) and oxygen storage capacity (OSC) measurements, the redox behaviour of a Pt/CeTbO_x catalyst is compared to that of a classic model TWC system: Pt/CeO₂. The results reported here show that the redox efficiency of the Pt/CeTbO_x catalyst is much better, especially at low temperature operation conditions such as those occurring during the cold start of engines. The catalyst containing terbium also shows lower ‘light-off’ temperatures for both methane and carbon monoxide oxidation.     

Characterizations of platinum catalysts supported on Ce, Zr, Pr-oxides and formation of carbonate species in catalytic wet air oxidation of acetic acid

Catalytic wet air oxidation (CWAO) of aqueous solution of acetic acid (78 mmol L⁻¹) was carried out with pure oxygen (2 MPa) at 200 °C in a stirred batch reactor on platinum supported oxide catalysts (Pt/oxide, oxide = CeO₂, Zr_0.1Ce_0.9O₂, Zr_0.1(Ce_0.75Pr_0.25)_0.9O₂ and ZrO₂). Platinum was loaded on oxides by impregnation (5 wt%), and then the catalysts were reduced under H₂. Homogenous dispersions of 2–3 nm metal crystallites were obtained. The catalytic activity depended on the ability of the support to resist to the formation of carbonates. Ce(CO₃)OH species, determined by FT-IR and XRD, were rapidly formed during the CWAO reaction especially on mixed oxides. These carbonates were responsible to a drastic drop in catalytic performances. Amounts of carbonate species increase with the ability of the catalyst to transfer oxygen.     

Oxygen storage capacity of promoted Rh/CeC2 catalysts. Exceptional behavior of RhCu/CeO2

The effect of various additives (V, Cr, Mn, Fe, Co, Ni, Cu and Pb) on the oxygen storage capacity (OSC) of CeO₂ and Rh/CeO₂ catalysts was investigated. Copper is an excellent promoter of OSC conferring to Rh a very high resistance to sintering (900°C, 2% O₂).     

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.     

Recent advances in automobile exhaust catalysts

Catalysts, which were recently developed by Toyota for the control of automobile exhaust, are reviewed. (1) For use in low emission vehicles, a CeO₂-ZrO₂ solid solution (CZ) with both high oxygen storage capacity and high heat resistance was developed as a support for a high performance three-way catalyst (TWC). (2) A novel three-way catalyst named the NO_x storage-reduction catalyst (NSR) was developed for automotive lean-burn engines. The NSR catalyst can store NO_x in an oxidizing atmosphere and then reduce stored NO_x at stoichiometric or reducing conditions. Also, it has high tolerance to sulfur poisoning which is the most stringent problem for the NSR catalyst.     

Oxygen Storage and Mobility on Model Three-Way Catalysts

Oxygen storage capacity (OSC) of TW catalysts has a strong impact on their performances under oscillatory conditions. This paper reviews the different methods developed for OSC measurements, the effects of catalyst composition on OSC as well as the impact of OSC on TW catalysis, concentrating on the results obtained in our laboratory. Use of OSC measurements for catalysts control (on-board diagnostic) is also examined. The role of superoxide species as intermediates in the oxygen storage process will be emphasized. Finally, we shall review the recent developments on CeZr-based oxides.     

Synthesis,characteristics, and redox properties of Zr/Sn-doped CeO2 nanoparticles in H2 gas at high temperatures

Metal(M = Zr, Sn)-doped CeO₂ nanoparticles were synthesized by a hydrothermal process to develop PdO@M-doped CeO₂ catalysts. The average particle size of both M-doped CeO₂ nanoparticles was under 10 nm, whereas the particle size reduced as the dopant concentration increased in the M-doped CeO₂ nanoparticles. The largest specific surface area was 226 m²/g in the Zr-doped CeO₂ nanoparticles. The particle morphology showed a spherical shape in both M-doped CeO₂ nanoparticles. The PdO@M-doped CeO₂ catalysts were then prepared by adsorbing Pd(OH)₂ onto the surface of M-doped CeO₂ nanoparticles by a precipitation method and synthesizing the catalysts by calcining at 500 °C for 3 h. The H₂ consumptions of the PdO@M-doped CeO₂ catalysts were characterized as the oxygen storage capacity at various temperatures. The results show that the oxygen storage capacities of the PdO@M-doped CeO₂ catalysts are superior to that of the pure CeO₂ catalyst at temperatures higher than 550 °C. The oxygen storage capacity of the PdO@Sn-doped CeO₂ catalyst is better than that of the PdO@Zr-doped CeO₂ catalyst.     

Regeneration of thermally aged Pt-Rh/CexZr1−xO2-Al2O3 model three-way catalysts by oxychlorination treatments

Pt-Rh/Ce_xZr_1−xO₂-Al₂O₃ with 0.6 and 1.0 wt.% noble metal loadings were prepared and characterized for their metal dispersion with respect to Ce_xZr_1−xO₂-free Pt-Rh/Al₂O₃ in fresh, thermally aged and oxychlorinated states. Thermal ageing at 973 K led to loss of metal dispersion in all cases but to negligible effect on the dispersion of the Ce_xZr_1−xO₂ component where present. Oxychlorination was able to fully recover metal dispersion in all cases but led to different effects on the redox properties of Ce_xZr_1−xO₂ which appeared to be related to the metal loadings. Despite showing improved dispersion following regeneration, higher loaded catalyst showed no improvement in light-off performance for either NO reduction or CO oxidation and showed poorer oxygen storage (OSC) ability, particularly at higher temperatures. Lower loaded catalyst showed improved dispersion, improved OSC and reduced light-off temperatures for NO reduction and CO oxidation after oxychlorination compared to that in the thermally aged state.