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 Properties of Ceria and CeO2-Containing Materials

Cerium dioxide (CeO2, ceria) is becoming an ubiquitous constituent in catalytic systems for a variety of applications. 2016 sees the 40th anniversary since ceria was first employed by Ford Motor Company as an oxygen storage component in car converters, to become in the years since its inception an irreplaceable component in three-way catalysts (TWCs). Apart from this well-established use, ceria is looming as a catalyst component for a wide range of catalytic applications. For some of these, such as fuel cells, CeO2-based materials have almost reached the market stage, while for some other catalytic reactions, such as reforming processes, photocatalysis, water-gas shift reaction, thermochemical water splitting, and organic reactions, ceria is emerging as a unique material, holding great promise for future market breakthroughs. While much knowledge about the fundamental characteristics of CeO2-based materials has already been acquired, new characterization techniques and powerful theoretical methods are dee...

Fundamentals and Catalytic Applications of CeO2-Based Materials

Use of CeO2-based oxides in the three-way catalysis

Automotive catalytic converters: current status and some perspectives

Oxygen vacancies in transition metal and rare earth oxides: Current state of understanding and remaining challenges

The reduction of CeO2 by hydrogen has been studied from 300–1200 K by several complementary techniques: temperature-programmed reduction (TPR) and magnetic susceptibility measurements, Fourier-transform infrared (FTIR), UV–VIS diffuse reflectance and X-ray photoelectron (XP) spectroscopy. Two CeO2 samples were used with B.E.T. surface areas of 115 and 5 m2 g–1, respectively. The concentration of Ce3+ was determined in situ by measuring the magnetic susceptibility and the CeIII photoemission line. The reduction began at 473 K, irrespective of the initial surface area of the ceria. In the case of the low-surface-area sample, an intermediate reduction step was observed between 573 and 623 K, corresponding to the reduction of the surface. This intermediate step was less easily observed in the case of the high-surface-area ceria. In both cases, the reduction led to a stabilised state with the formal composition CeO1.83. Temperatures higher than 923 K were required to reduce the ceria further. The surface CeIII content determined by XPS was close to that determined by magnetic susceptibility measurements. The intensity of the 17 000 cm–1 band in the UV–VIS reflectance spectrum also varied with the degree of reduction. Finally, the evolution of the surface species observed by IR spectroscopy was in good agreement with the results from the other techniques. The IR results indicated large changes in the concentration and nature of both the hydroxyl and the polydentate carbonate species during the reduction process. The adsorption of oxygen on samples previously reduced to the composition CeO1.83 led to almost complete reoxidation at room temperature. The state of the initial B.E.T. surface did not influence the oxidation process. A slight excess adsorption of oxygen was evident on the surface. This was thermodesorbed at 380 K under vacuum.

Reduction of CeO2 by hydrogen. Magnetic susceptibility and Fourier-transform infrared, ultraviolet and X-ray photoelectron spectroscopy measurements

Successive reduction steps of CeO2 particles by hydrogen between 300 and 1070 K have been followed by temperature-programmed reduction (TPR) and in situ magnetic measurements on several samples with different BET surface areas. The nature of the phases present in cerias reduced between 670 and 1270 K was determined by X-ray analysis. Finally, reoxidation by oxygen or air was studied at room temperature for all the reduced samples.Magnetic and TPR results show a direct relationship between the degree of reduction and the BET surface area. Indeed, for most of the samples, the degree of reduction at 620–670 K determined by magnetism corresponded to the creation of one layer of Ce3+ ions at the surface of the ceria. A similar relationship between the BET surface area and the extent of reduction was established using the area of the low-temperature TPR composite peak, the maximum of which was found to be constant at 810 K.When the reduction progresses further into the bulk, two main phases were evidenced: first, and expanded cubic CeO2 –x phase derived from the initial ceria by a dilatation of the whole structure and, for deeply reduced samples, the hexagonal Ce2O3 phase. A new intermediate phase, cubic Ce2O3, was also observed on samples reduced at 1070–1170 K.Complete reoxidation by oxygen occurs at room temperature, for all reduction percentages below ca. 60 %, i.e. as long as the reduced phase remained in the cubic form. When the hexagonal Ce2O3 phase has been formed, the reoxidation cannot be completed at 294 K.

Reduction of cerias with different textures by hydrogen and their reoxidation by oxygen

The influence of a reducing atmosphere on the thermal stability of CeO2 was studied on a high surface area ceria sample (115 m2 g−1) treated 2 h under hydrogen or carbon monoxide at various temperatures between 673 and 1123 K. Comparative experiments were done under air or vacuum, and also in presence of water or carbon dioxide in order to estimate the relative importance of the reduction products. An important decrease of the specific surface area was observed between 850 and 1000 K under air, vacuum, carbon monoxide or water pressure, the residual BET area being below 10 m2 g−1 at 1100 K. Under hydrogen, the same loss of surface was obtained at ca. 150 K lower temperatures. In all cases, the first step was the elimination of the microporosity followed by the growth of the crystallites. The peculiar influence of hydrogen was related to the high concentration of lattice oxygen vacancies created during the reduction of the bulk. In the case of carbon monoxide atmosphere which also reduces the sample, the carbonate species formed during the reduction are eliminated from the bulk at higher temperatures, which explain the better resistance to sintering compared to hydrogen. This was confirmed by a treatment under carbon dioxide atmosphere which was found to preserve the specific surface area better because of the stabilization of the carbonate species on the ceria.

Ahmidou Laachir

Papers

Reduction of CeO2 by hydrogen. Magnetic susceptibility and Fourier-transform infrared, ultraviolet and X-ray photoelectron spectroscopy measurements

Reduction of cerias with different textures by hydrogen and their reoxidation by oxygen

Thermal stability of a high surface area ceria under reducing atmosphere

Reduction of CeO2 by Hydrogen. Magnetic Susceptibility and Fourier- Transform IR, UV and X-Ray Photoelectron Spectroscopy Measurements.