Oxygen Storage Capacity Performance Research Articles

A proxy for oxygen storage capacity from high-throughput screening and automated data analysis.

Oxygen storage and release is a foundational part of many key pathways in heterogeneous catalysis, such as the Mars-van Krevelen mechanism. However, direct measurement of oxygen storage capacity (OSC) is time-consuming and difficult to parallelise. To accelerate the discovery of stable high OSC rare-earth doped ceria-zirconia oxygen storage catalysts, a high-throughput robotic-based co-precipitation synthesis route was coupled with sequentially automated powder X-ray diffraction (PXRD), Raman and thermogravimetric analysis (TGA) characterisation of the resulting materials libraries. Automated extraction of data enabled rapid trend identification and provided a data set for the development of an OSC prediction model, investigating the significance of each extracted quantity towards OSC. The optimal OSC prediction model produced incorporated variables from only fast-to-measure analytical techniques and gave predicted values of OSC that agreed with experimental observations across an independent validation set. Those measured quantities that feature in the model emerge as proxies for OSC performance. The ability to predict the OSC of the materials accelerates the discovery of high-capacity oxygen storage materials and motivates the development of similar high-throughput workflows to identify candidate catalysts for other heterogeneous transformations.

Effect of analyzer scan time on the oxygen storage capacity performance in Pd-based TWCs

Effect of analyzer scan time on the oxygen storage capacity performance in Pd-based TWCs

Enhanced thermal stability and oxygen storage capacity of ceria-zirconia prepared by flame spray pyrolysis under high temperature

Ceria zirconia solid solution with high oxygen storage capacity (OSC) and thermal stability under 1000 ​°C is quite important for support materials in three-way catalysts (TWCs). In this work, Ce1-xZrxO2 with different Zr dopants (x ​= ​0, 0.125, 0.250 and 0.375) have been prepared by flame spray pyrolysis (FSP) with carboxylic acid or ethanol and carboxylic acid (v:v 1:4) solvents. The influences of Zr content and the addition of ethanol into carboxylic acid on the OSC performance and thermal stability have been systematically characterized by X-ray diffraction (XRD), N2 adsorption-desorption, Raman analysis, field emission scanning electron microscope (FESEM), high resolution transmission electron microscope (HRTEM), X-ray photoelectron spectroscopy (XPS), hydrogen-temperature programmed reduction (H2-TPR), and pulse thermal analysis using H2 as reducing agent. The presence of cubic-tetragonal interfaces in the Ce0.750Zr0.250O2 sample can enhance the formation of oxygen vacancies and the mobility of lattice oxygen in ceria-zirconia solutions, which results in the largest OSC (349 ​μmol ​g−1) among the fresh samples. The cubic-tetragonal interfaces in the Ce0.750Zr0.250O2 sample can also promote the thermal stability under 1000 ​°C to preserve better OSC (202 ​μmol ​g−1) than other aged samples. Furthermore, after adding with ethanol into carboxylic acid solvent, the OSC of the sample further increases to 371 ​μmol ​g−1 for the increment of oxygen vacancy concentration. It is worthy to note that the introduction of ethanol can suppress Zr migration from the lattice to the surface of CeO2 at high temperature, further enhancing OSC (240 ​μmol ​g−1) and thermal stability.

Aluminium doped ceria–zirconia supported palladium-alumina catalyst with high oxygen storage capacity and CO oxidation activity

The Ce0.5Zr0.3Al0.2O1.9/Pd-γ-Al2O3 catalyst prepared by a mechanochemical route and calcined at 1000°C for 20h in air atmosphere to evaluate the thermal stability. The prepared Ce0.5Zr0.3Al0.2O1.9/Pd-γ-Al2O3 catalyst was characterized for the oxygen storage capacity (OSC) and CO oxidation activity in automotive catalysis. For the characterization, X-ray diffraction, transmission electron microscopy and the Brunauer–Emmet–Teller (BET) technique were employed. The OSC values of all samples were measured at 600°C using thermogravimetric-differential thermal analysis. Ce0.5Zr0.3Al0.2O1.9/Pd-γ-Al2O3 catalyst calcined at 1000°C for 20h with a BET surface area of 41m2g−1 exhibited the considerably high OSC of 583μmol-Og−1 and good OSC performance stability. The same synthesis route was employed for the preparation of the CeO2/Pd-γ-Al2O3 and Ce0.5Zr0.5O2/Pd-γ-Al2O3 for comparison.

Preparation and characteristics of nano-crystalline Cu-Ce-Zr-O composite oxides via a green route: supercritical anti-solvent process

The nano-crystalline Cu-Ce-Zr-O composite oxides were successfully prepared by the supercritical anti-solvent (SAS) process. The physicochemical properties and catalytic performances were investigated by X-ray diffraction (XRD), Raman spectroscopy, H2 temperature-programmed reduction (H2-TPR), oxygen storage capacity (OSC) measurement and catalytic activity evaluation. It was found that Cu2+ ions incorporated into CeO2-ZrO2 lattice to form Cu-Ce-Zr-O solid solution associated with the formation of oxygen vacancies. The Cu-Ce-Zr-O catalysts prepared via the SAS process with the Cu content 2.63 mol.% showed the highest OSC index of 636.9 μmol/g. Compared with the samples prepared by impregnation method, Cu doping using SAS process could improve the dispersion of Cu2+ in the composite oxide, enhance the interaction between Cu2+ and CeO2-ZrO2, improve the reducibility of catalyst, and thus improve the OSC performance and increase the catalytic activity for CO oxidation at low temperature.

Aluminum-doped ceria-zirconia solid solutions with enhanced thermal stability and high oxygen storage capacity

A facile solvothermal method to synthesize aluminum-doped ceria-zirconia (Ce0.5Zr0.5-xAlxO2-x/2, x = 0.1 to 0.4) solid solutions was carried out using Ce(NH4)2(NO3)6, Zr(NO3)3·2H2O Al(NO3)3·9H2O, and NH4OH as the starting materials at 200°C for 24 h. The obtained solid solutions from the solvothermal reaction were calcined at 1,000°C for 20 h in air atmosphere to evaluate the thermal stability. The synthesized Ce0.5Zr0.3Al0.2O1.9 particle was characterized for the oxygen storage capacity (OSC) in automotive catalysis. For the characterization, X-ray diffraction, transmission electron microscopy, and the Brunauer-Emmet-Teller (BET) technique were employed. The OSC values of all samples were measured at 600°C using thermogravimetric-differential thermal analysis. Ce0.5Zr0.3Al0.2O1.9 solid solutions calcined at 1,000°C for 20 h with a BET surface area of 18 m2 g−1 exhibited a considerably high OSC of 427 μmol-O g−1 and good OSC performance stability. The same synthesis route was employed for the preparation of the CeO2 and Ce0.5Zr0.5O2. The incorporation of aluminum ion in the lattice of ceria-based catalyst greatly enhanced the thermal stability and OSC.

Microstructure and oxygen storage capacity of Sr-modified Pt/CeO2–ZrO2 catalysts

Strontium was introduced into CeO2–ZrO2 mixed oxides (CZ) by doping and impregnation methods, and then Pt was impregnated on the Sr-modified CZ to obtain the catalysts. X-ray diffraction (XRD), X-photon spectra (XPS), high-resolution transmission electronic microscopy (HRTEM) and H2 temperature programmed reduction (TPR) were carried out to characterize the micro-structure and reducibility of catalysts. The oxygen storage capacity (OSC) was evaluated with CO serving as probe gas. The results showed that the incorporation of Sr2+ in the lattice of CZ could promote the OSC properties by increasing the structure defects and enhancing the diffusion rate of oxygen from bulk to surface. For the Sr-impregnated sample, the strong metal–support interaction (SMSI) between Pt and CZ was interrupted, since Sr covered partial surface Ce species. Such interruption retarded the back-spillover effect occurring at the Pt/Ce interface at low temperature, resulting in the loss of OSC. Meanwhile, it was found that a part of impregnated Sr2+ could partially diffuse from the surface to the inner atomic layers of CZ and partially incorporated in the lattice during the calcination. The OSC performance of Sr-impregnated sample therefore climbed remarkably with the rise of temperature.

Modification of CeO 2–ZrO 2 mixed oxides by coprecipitated/impregnated Sr: Effect on the microstructure and oxygen storage capacity

Strontium was introduced to modify CeO 2–ZrO 2 mixed oxides (CZ) by two methods, coprecipitation (CZS) and impregnation (SCZ). Structural and textural characterizations revealed that Sr could retard the sintering of oxide particles and restrict the phase segregation during the hydrothermal ageing treatment. Specifically, the impregnation method brought about a more satisfying thermal stability of the modified CZ. This phenomenon was attributed to the enrichment of Sr on the particle surface and the formation of SrZrO 3 phase. The reducibility of the oxides was investigated by means of the oxygen storage capacity (OSC), and aged SCZ (SCZa) presented the best OSC performance. The reduction-ratio-dependent activation energy ( E a) was extremely low for the surface reduction of SCZa, suggesting the participation of highly active oxygen. The SrZrO 3/CeO 2–ZrO 2 interface was considered as the possible origin of this oxygen species. During bulk reduction, the effect of Sr on enhancing the reducibility was evident as well.

Investigation of the OSC performance of [formula omitted] catalysts by CO oxidation and 18O/ 16O isotopic exchange reaction

The development of a more efficient oxygen storage material is a very important approach for the optimization of automotive catalysts. To investigate the influence of the physical parameters, the Pt particle size and specific surface area (SSA) on the OSC (oxygen storage capacity) performance of the Pt / CeO 2 – ZrO 2 – Y 2 O 3 (CZY) catalysts, a series of Pt/CZY catalysts were prepared and characterized. The OSC performance was evaluated by CO oxidation from 200 to 400 ∘ C , while alternately feeding CO ( 2.0 vol % ) / N 2 and O 2 ( 1.0 vol % ) / N 2 for 60 s at a flow rate of 7.0 l/min. The CO 2 generation was analyzed continuously and used to indicate the OSC performance and oxygen storage/release behavior. The oxygen surface diffusion and bulk diffusion rates on the catalysts were further characterized by the O 18 / O 16 isotopic exchange reaction and correlated with the OSC performances. The characterization results of the Pt particle size and SSA of the Pt/CZY catalysts indicated that the Pt particle size and SSA of Pt/CZY appeared to be a hyperbolic distribution, being interdependent and difficult to control independently. OSC performance results by CO oxidation at 200 and 300 ∘ C showed that smaller Pt particle size favored OSC performance and appeared to be the optimum around 70 m 2 / g for the SSA. This corresponds with the oxygen mobility results obtained from the O 18 / O 16 isotopic exchange reaction at 400 ∘ C , that is, the oxygen surface and bulk diffusion showed a peak at the Pt particle size of 6 nm and an SSA of 40 m 2 / g .

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.

Atmospheric pressure solvothermal synthesis of ceria–zirconia solid solutions and their large oxygen storage capacity

Ceria–zirconia solid solution has a function as an oxygen storage material, which keeps air to fuel ratio (A/F) on a stoichiometric composition at the surface of three-way catalyst (TWC) for automotive exhaust. When A/F could be kept stoichiometric, TWC shows good catalytic activity. At first, ceria which dissolves 20 mol% of zirconia was developed by Ozawa et al. in 1987. After that, the ceria–zirconia solid solution was improved to achieve a complete solubility in the solid state at nano-level by surfactant modified homogeneous coprecipitation (J catal 169:490, 1997). Nano-level solid solution of ceria and zirconia could have been made by various methods. Those materials have similar amount of oxygen storage capacity (OSC). The improvement of OSC comes from the larger amount of bulk oxygen that can contributes OSC by the larger amount of zirconia dissolving into ceria (Catal Lett 33(1–2):193–200 1995). Solvothermal synthesis is usually done in a higher temperature than that can be reached under atmospheric pressure. The higher temperature accelerates generation of precipitation; however, a pressure vessel is necessary, and such a hermetically closed system is unsuitable to the material synthesis of the low-value-added product. Atmospheric pressure solvothermal (APS) synthesis was applied to ceria-zirconia solid solutions in this study. The APS ceria-zirconia showed larger amount of OSC. The excellent OSC performance was presumed to come from further uniformity of zirconium ions in the ceria lattice.

Effect of the Amount of Pt Loading on the Oxygen Storage Capacity of Ceria-Zirconia Solid Solution

As an important oxygen storage material, ceria-zirconia solid solution is widely used in automotive three-way catalysts. For the Ce-Zr solid solution being usually used with a noble metal, the evaluation of oxygen storage capacity (OSC) should be conducted with the Ce-Zr solid solution loaded with a noble metal. The measured OSC of noble-metal-loaded Ce-Zr solid solution consists of two parts: the stored oxygen within the solid solution itself and the adsorbed oxygen on the loaded noble metal particles. Therefore, it is very necessary to clarify the influence of metal loading on the measured OSC in order to ascertain the exact OSC of the solid solution itself. In this research, the authors attempted to clarify the above issues by characterizing the OSC performance of Ce-Zr solid solutions with platinum (Pt) loading from 0.0001-10 mass%. We found that increasing the amount of Pt loading increases the oxygen storage and release rates and that increasing the temperature also increases the oxygen storage rate, although the oxygen release rate is not affected by increasing the temperature. The apparent OSC reached saturation over a certain amount of Pt loading and temperature. The saturated OSC increased with increasing temperature.

ナノメータコンポジット材料 白金／セリア‐ジルコニア固溶体微粒子の酸素貯蔵能に及ぼす白金担持量の影響

Ceria-zirconia (Ce-Zr) solid solution is widely used as an oxygen storage material, which is a key component in the automotive three-way catalysts. The Ce-Zr solid solution is usually used with noble metals supported on their surface. Thus the evaluation of oxygen storage capacity (OSC) should be conducted on the Ce-Zr solid solution loaded with a noble metal. The measured OSC of noble-metal-loaded Ce-Zr solid solution consists of two parts; one is the stored oxygen within the solid solution itself, and the other is the adsorbed oxygen on the surface of the supported noble metal particles. Therefore, it is necessary to clarify the influence of the noble metal on the measured OSC, and this will also help to ascertain the exact OSC of the solid solution itself. In this research, the authors tried to clarify the above issues by characterizing the OSC performance on Ce-Zr solid solutions with Pt loading from 0.0001 to 10 wt%. We found that, increasing the Pt loading makes the oxygen storage and release rate higher. Temperature increase also makes the oxygen storage rate higher, however, the oxygen release rate is not affected by the temperature. The apparent OSC saturated above a certain level of Pt loading and temperature. The saturated OSC increased with increasing temperature.